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

[Orion]

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.

I get blobs of something when adding ammonia the first time. It happens at pH levels too low to be harmalas, the same as seen in the video in Q21Q21's post above. I assume this is some kind of magnesium salt? I could probably remove at least the visible stuff by filtering this off before going high with the pH. I have a slight concern that it may have an effect like I described at the end of the first post in this thread regarding excess sodium bicarbonate trapping alkaloids: Rue to separated freebases with less fuss.

After doing a manske on the entire precipitate and then basing again, there was nothing strange about the precipitation and I was able to get different fractions out with a clear pH gap between.

So I'm wondering, do I do the same thing again with this higher pH crashed portion of it, or go straight to manske? I'm feeling like a manske makes more sense, that way the one and only basing should be cleaner as the magnesium salts will already be disposed of.

As for the phosphoric acid approach, I could try that on another batch. It does seem like a manske takes care of the strange globs but one less step would be nice.

 

[Transform]

I get blobs of something when adding ammonia the first time. It happens at pH levels too low to be harmalas, the same as seen in the video in Q21Q21's post above. I assume this is some kind of magnesium salt? I could probably remove at least the visible stuff by filtering this off before going high with the pH. I have a slight concern that it may have an effect like I described at the end of the first post in this thread regarding excess sodium bicarbonate trapping alkaloids: Rue to separated freebases with less fuss.

After doing a manske on the entire precipitate and then basing again, there was nothing strange about the precipitation and I was able to get different fractions out with a clear pH gap between.

So I'm wondering, do I do the same thing again with this higher pH crashed portion of it, or go straight to manske? I'm feeling like a manske makes more sense, that way the one and only basing should be cleaner as the magnesium salts will already be disposed of.

As for the phosphoric acid approach, I could try that on another batch. It does seem like a manske takes care of the strange globs but one less step would be nice.

Sounds like the globs were most likely magnesium hydroxide, if they formed around the drops of ammonia. Were you able to observe closely how the precipitate formed?

I'd be inclined to agree that going straight to a Manske after the Mg reduction would appear to make sense. I've seen contradictory reports on whether Manske works for THH or not, however. I've not tried it, since the MAP approach provided freebase rather easily - can anyone else comment on practical results of attempting Manske on THH?

 

[Orion]

Sounds like the globs were most likely magnesium hydroxide, if they formed around the drops of ammonia. Were you able to observe closely how the precipitate formed?

I'd be inclined to agree that going straight to a Manske after the Mg reduction would appear to make sense. I've seen contradictory reports on whether Manske works for THH or not, however. I've not tried it, since the MAP approach provided freebase rather easily - can anyone else comment on practical results of attempting Manske on THH?

I'll probably do that. I might try to reduce it a bit more by adding more vinegar and magnesium, chopped into the smallest pieces I can before spinning it at high speed. The reason being I expect to see some color difference by now under UV, since this was the redissolved product which only precipitated at a pH above 9.5. Hopefully after freebasing and rinsing with basic distilled water again I can actually see a difference this time.

I assume the bubbling is just hydrogen gas and isn't a crucial component of the reduction, correct?

As for the blobs, they form exactly like they do in the video in Q21Q21's post. As soon as the ammonia drop hits the solution, a white substance forms around it and stays there, spinning around in the solution before it has began to cloud up at higher pH when the actual harmalas crash.

 

[Flufferus]

this is a cool thread. i would be so hype if i could make clear harmala crystals like that!!

 

[Orion]

Welp, strange things happened with a manske on the second reduction. As before, dark brown material appeared as the solution became saturated with salt. This time I removed it by filtering before the solution cooled enough to crash anything. I dissolved it on it's own in some vinegar and checked the fluorescence under UV. Same color as always.

The salt saturated solution is also the same color under UV. It looks like removing the dark material has depleted it of any harmalas. I had to get it ridiculously saturated in order for anything to precipitate, but it seems I have only salt, meaning the goodies were inside the dark material. I've already seen what happens when redissolving and basing that stuff. This solution stays cloudy and it looks like fresh orange juice. Possibly something to do with magnesium? The previous manske after dissolving the base precipitated product was clear. It has strange results at either stage in my experience.

 

[Transform]

I assume the bubbling is just hydrogen gas and isn't a crucial component of the reduction, correct?

Yes, the bubbling actually counts as unavoidably wasted reagent, since the real business is occurring via electron transfer at the metal surface. You'll be wanting those electrons to be going, as much as possible, into the harmaline molecules, whether or not that involves the intercession of single hydrogen atoms. Ergo, spinning the reaction nice and fast is the right way to go as that will maximise turnover of the harmaline at the reaction surface, as well as providing an ongoing supply of protons from the acidic environment, which drive the redox reaction forward.

As far as I'm aware at present, the idea of nascent hydrogen is now considered outdated pseudoscience, but the exact mechanism of is still poorly understood, although it's always possible that recent research may have brought some new level of insight.

What I'm saying here is that I'm willing to accept that atomic hydrogen formed from hydrated protons at the metal surface may be taken up directly by the harmaline within reach of any given hydration sphere - which, incidentally, is subtly different from a solvated electron - and/or electrons will be released from the metal surface directly into harmaline molecules during harmaline/metal collisions, and/or monatomic hydrogen will be picked up directly at the metal surface during collisions with harmaline molecules.

People cleverer than me would set up calculations to model stuff like this.

It may also be worth trying the reaction by dripping the acid in slowly, which may help to reduce losses which occur through evolution of gaseous hydrogen.

 

[Orion]

An observation on purity levels affecting precipitation: When separating a previous batch of harmalas there was a continuum of precipitation from as high as 7.8 to 8.3. This is in line with what is decribed in Q21Q21's separation method in the wiki version of their recent tek. They mentioned it can get even higher, as far as pH 9.1. This could be due to impurities or some salt remaining even after freebasing again after a manske. There was seemingly a lot of harmine and very little harmaline in my test and I knew something was off. I soon corrected this.

This time after dissolving the 'harmine' fraction in distilled vinegar, topping up with distilled water and adding ammonia I got clean separations at exactly 7 and 8, with no mixed fraction between. I didn't raise the pH beyond the crash points, just stabilized them at the pH they dropped out at. I will probably combine this harmaline with previous batches and continue to purify it further.

I now suspect there was more than a little harmine in my harmaline before I started the reduction to THH. Looks like it might take more purification before I begin the conversion.

I think we should be looking for a very clear gap between the separations and very little to no mixed fraction in between. Even with a very good pH meter and careful measuring, small amounts of impurities or salt can throw the precipitation points out of whack with a fair degree of overlap.

 

[Transform]

An observation on purity levels affecting precipitation: When separating a previous batch of harmalas there was a continuum of precipitation from as high as 7.8 to 8.3. This is in line with what is decribed in Q21Q21's separation method in the wiki version of their recent tek. They mentioned it can get even higher, as far as pH 9.1. This could be due to impurities or some salt remaining even after freebasing again after a manske. There was seemingly a lot of harmine and very little harmaline in my test and I knew something was off. I soon corrected this.

This time after dissolving the 'harmine' fraction in distilled vinegar, topping up with distilled water and adding ammonia I got clean separations at exactly 7 and 8, with no mixed fraction between. I didn't raise the pH beyond the crash points, just stabilized them at the pH they dropped out at. I will probably combine this harmaline with previous batches and continue to purify it further.

I now suspect there was more than a little harmine in my harmaline before I started the reduction to THH. Looks like it might take more purification before I begin the conversion.

I think we should be looking for a very clear gap between the separations and very little to no mixed fraction in between. Even with a very good pH meter and careful measuring, small amounts of impurities or salt can throw the precipitation points out of whack with a fair degree of overlap.

What were the concentrations of each of the components in this last, clear separation which you've described here?

I struggle to see why salt would affect the precision of separation, so it leads me to think what other impurities could play such a role - pectin-like substances, perhaps?

 

[Orion]

What were the concentrations of each of the components in this last, clear separation which you've described here?

I struggle to see why salt would affect the precision of separation, so it leads me to think what other impurities could play such a role - pectin-like substances, perhaps?

I wasn't being too exact but it was 16g of a dark orange mix of harmalas dissolved in roughly 100ml of vinegar topped up with around 600ml of distilled water. I filtered the solution before basing but there was very little crud in it, too little to retrieve and measure.

You may be right about pectin. I've done two recent extractions - one using NaOH as a base with another 10 full jars worth of water rinses and another using only ammonia as a base in the freebasing and some in the rinses. Both were collected and dried, mansked, based and redissolved before separating with ammonia. The product of both extractions behaved the same when separating for the first time.