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TEK Stoney Harmalas Process

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Transform said:
wtf, they look like magnesium sulfate or something! Are you sure that's harmalas? Fml :ROFLMAO:
Lovely work if it is, but yeah, just… wow!
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Lol. Funny but i added no magnesium to my harmalas acetate before adding sulfuric acid, i know this level off purity is hard to understand for some but this is truly what a clean sulfate extract crystallization looks like, and in fact I can be seem with UV, harmala sulfates have less florescence, but when you add acetic to the mix the very bright notable UV florescence is observed.
 
Varallo said:
Ready to share amounts and or concentrations😃?
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I just added a dropper full of concentrated sulfuric to a concentrated solution (made by washing fb with water, decanting aqueous, and adding acetic until loosely dissolved and uv florescent, and added a dropper full of sulfuric. I usually do my work wet without filtering or weighing in between unless it's stoichiometric synth work or precise recrystallization. I keep my salts in liquids until they are crystals.
 
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Transform said:
Replication is the only way… no hints available even for the volume of concentrated harmala solution? We need all the help we can get 🥺 lol
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Like I said I just pour off as much water as possible from fb precipitate, add glacial acetic acid in drops until uv is bright, and then hit 1 full dropper of sulfuric. I'll do more replications and contnue crystal work to get more results and measurements, i started processing a large extraction mass recently.

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2x rinsed Fb, needs more rinses and hcl salting and nacl rinsing, then I'll do some cleanup and weigh the fb, take pics of the workup, and results. I'll keep you guys posted.
 
I haven't had any luck with IPA. The acetate salt is very soluble in water and forms a thick liquid when most of the water is evaporated. I had about 5g of harmalas, dissolved them in acetic acid, reduced the volume to less then 25ml, added about 10ml IPA, nothing happened. I added another 15 and still nothing. I put it in the fridge, and still nothing. HCl salt is much less soluble compared to acetate, I added about 40ml IPA to a 50ml solution and almost everything crashed out, but those were normal greenish yellow crystals.
 
Still in the midst of processing and my recycling flask (for harmalas washed phases crystalized out, honestly it's difficult not to get awesome crystals when you touch sulfuric acid into the process,) still fighting the good fight, processing data, I'll update soon, but patience is a virtue.

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Tested UV fluorescence, amazing how my quick and careless washes throw out so much alkaloid but I am processing 2 pounds of seeds and sulfate crystals do weigh more due to the clunky acid size, but damn those crystals don't lie, some sexy harmalas. Maybe I'll try doing half of these into an acetate/ethanol workup (which is gonna take some time given my ethanol depletion from all my recent works), and half resalted to Hcl so some people won't have to ask what color harmalas HCL is supposed to be.


Also here's some freebase I've been cleaning.
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So, sulfuric acid did the trick for me! I added 1-2ml of concentrated sulfuric acid to 5g of harmine freebase, it reacted violently, producing some fumes (just a little). I got scared and added some water, then I added some more dilute sulfuric acid, I had to heat the solution up to make everything dissolve. The solution was strongly acidic, I had added too much acid... But in any case, I reduced the volume to about 50ml and then added 25ml IPA. Over the next 1 hour, pretty needless crystallized out of the solution. They are still pretty greenish in color, but that's likely because my harmine wasn't very "color free".
I don't think everything crystallized out of the solution and will check the weight later. I will try to redissolve and recrystallize and see how it goes. I'm also wondering if the sulfate could directly be dissolved in and recrystallized from IPA.
In any case, the sulfate looks nice, much better than the HCl. I had trouble properly crystallizing the HCl, harmaline HCl produced beautiful needles but harmine HCl just won't... It kept crashing out as a powder all together. Anyways, will report back soon.
 
Wait, does this mean we can do a sulfate Manske-style precipitation by using sodium or potassium sulfate solution, with the harmalas in aqueous acetic acid as per the NaCl version?

Sulfuric acid is clearly rather convenient (no excess metal ions, for one), but not everyone has access to it. It's strictly controlled in Germany and probably a few other EU states as mentioned in a video I posted a little while ago.
 
Yes, you're right about the availability of ≤15% H₂SO₄. I'm currently mentally weighing up the relative convenience of adding ~5.5 parts of water for every part of acid, versus however much it takes to dissolve a comparable molar amount of a sulfate salt. Sodium bisulfate might be worth a try. If we get quantitative data for the solubility of harmala sulfates, it would be good to be able to square it up against these figures for NaHSO₄:
Solubility in water28.5 g/100 mL (25 °C)
100 g/100 mL (100 °C)
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So I checked the weight and nearly everything had crystallized out. I redissolved the crystals (nearly 6g but still with excess h2so4) in hot water to make a 50ml solution, I added 25ml of IPA, but nothing happened! I then reduced the volume to around 30ml, added 20ml IPA and now after 2 days, I see one small cluster of needles but nothing else.
I'm thinking that the excess sulfuric acid in earlier solution had produced isopropyl sulfate, which significantly reduced the solubility. The isopropyl sulfate remained dissolved in the solution, likely because of the very low pH. Later, when I poured the liquid off and added NaOH to it, the two phases separated. A transparent aqueous phase with very little color, and a dark reddish brown top layer. The top layer was acidic and the bottom basic... Sodium sulfate settled at the bottom and wouldn't dissolve (because of the high pH?). Upon heating, the upper layer evaporated, leaving behind dark brown stuff. Upon further addition of NaOH, a small amount of light tan harmine freebase (or a look alike) crashed out, and the dark brown stuff coagulated into small hard pellets. The light tan stuff did not settle at the bottom but swam at the top.
I think washing aqueous solution of harmala salts with ethylacetate could be interesting.
 
So I made another attempt, reduced the volume to the point of saturation (around 20-25ml), added IPA to reach 50ml. Crystallization was relatively better, but I think no more than half of the total amount has crashed out.
This has lead me to think about alternative explanations. I think the better recrystallization last time was primarily due to a significant excess of sulfuric acid. I think the acid ions push out the harmala salts, similar to salt ions in case of manske. I think glacial acetic acid is the key factor in StoneyBroski's method. The excess acetic acid reduces the solubility of harmala salts.
 
Another update: manske works with sodium sulfate as well. I added excess amount of sodium sulfate to a harmine acetate solution, and harmine sulfate crystallized out. I also tried recrystallizing harmine sulfate with sodium sulfate, it works but the ratio of both solutions is different, I will try to work out the exact ratios.
 
Jan e Kharabat said:
Another update: manske works with sodium sulfate as well. I added excess amount of sodium sulfate to a harmine acetate solution, and harmine sulfate crystallized out. I also tried recrystallizing harmine sulfate with sodium sulfate, it works but the ratio of both solutions is different, I will try to work out the exact ratios.
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Thanks for trying this out - I hope we'll soon see some further replications from other forum members (such as myself). Putting some definite figures to both variants of the sulfate Manske (Janske :D ?) will be a valuable addition to the literature.

One slightly obscure drawback might be that a few microorganisms do use sulfate as a macronutrient, but typically only under anaerobic conditions.
 
Another interesting thing I noticed is that the acetate salt breaks down into freebase upon heating. I forgot a solution on the heating plate, the temp must've have been around 140 max, the resulting powder would not dissolve in water and I was scared that I had burnt it, but then I added some acetic acid and it redissolved.
 
Jan e Kharabat said:
Another interesting thing I noticed is that the acetate salt breaks down into freebase upon heating. I forgot a solution on the heating plate, the temp must've have been around 140 max, the resulting powder would not dissolve in water and I was scared that I had burnt it, but then I added some acetic acid and it redissolved.
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While not an altogether surprising observation once we consider the analogous thermal freebasing of DMT acetate alongside the lower basicity of harmaline and, particularly, harmine, this is indeed very useful to know. I'd say it deserves its own write-up, and a cross-reference in the 'DMT acetate to freebase' threads.
 
So... directly adding solid sodium sulfate, 10g per 100ml of Harmala solution, doesn't crash out all the harmalas, but adding a saturated solution of sodium sulfate equal to the volume of harmala solution works really well, but takes up to a day or 2 (3 just to be sure) to crystallize everything. But the crystals are really pretty! I had even better looking ones in the previous run but didn't take any Fotos. I must say, the greenish tint is still there, so... OP must have done a whole lot of Manskes to get those really white crystals. Nevertheless, I have never had such pretty crystals with HCl!
Also, converting acetate to sulfate doesn't work that straightforwardly. Adding a saturated solution of sodium sulfate converted about 80% of the harmala acetate to sulfate. The other 20% remained in acetate form. I filtered out the Harmala sulfate, based the mother liquor, collected the freebase, redissolved in acetic acid, and repeated the Manske, more Harmala sulfate crashed out! There is likely still more actetate left, I will try to calculate how much.
 

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