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Ethyl Acetate Approach for Harmala

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Nachooo said:
Thanks for this Tek. I am really tired of waiting days for all those filtering and manske steps in the traditional extraction tek. Also I think lot of product is lost in all those filtration steps through cotton, coffee filters etc... and your approach helps a lot with that.

I think that the EA tek can be used also with dry ephedra powder..Used the CIELO tek adapted..although I salted it with HCL acidified water (read somehwhere that ephedrine citrate was not crystals)...got some kind of orange resin almost crystalline that was positive to ephedrine with reagent
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Water from the dilute HCl may be interfering with xtals precipitating. Other organic acids can be used (fumaric, malic, etc) if you verify citric does not give xtals.

Also, there is a chance that HCl reacts with ethyl acetate over time. Less of an issue if dilute. I would stick to crystalline organic acids soluble in EA, some of them could work.
 
The preliminary results and lab results are very very promising but i dont think enough people have reported their results to confirm my findings.
There's a few things that need ironing out but it definately works and is fast. I think it'll come down to how clear the process has been written up (if its easy to follow) and if others are having the same results before someone authorizes a wiki page.

I don't know what the wiki process is, i should add i'm surprised Brennendes Wasser bufo tek doesn't have its own page either.
 
I wouldn't be surprised if the manske isn't necessary. And that seems like a very simple tek. From my experience i don't agree with not grinding, I get a higher yeild when grinding and i believe others have found this too.
The big question would be what his yield is. But it sounds like its good to go. The LC-MS results would be interesting to see with his process.

My biggest thing with the ea harmala approach was also to eliminate manske steps which IME was affecting yields and taking far too long.
 
Haha I would agree Cheelin that's why i trialed the EA Harmala approach. There will always be something better and more simple around the corner. That is what is so good about this community and the side of the community I like the most, that is to say the experimental, technical and research threads.

I guess if you wanted the EA harmala approach simpler you could stop the tek at the EA salting step for harmala citrate (if one was only using it for pharma).
 
BW's method definitely works great, if you want something simple.
Yield is not the highest possible with it as grinding the seeds yields few percent more, but still fine for all practical purposes.
 
It's not especially quick as you still need to wait for settling of alkaloids in each cycle. Imo this is very convenient for anyone with family and work, most of the time is just passive waiting.
 
In cognizance of this thread, and having a sample of ammonia-precipitated crude rue alks at hand, I decided to test their solubility in butyl acetate. It turns out that despite being a fine powder the alkaloids are only difficultly soluble in that solvent. It looks as though a little something did dissolve though.

Further investigations will be carried out see whether this turns out to be a way of separating the harmala alkaloids to some degree. There aren't any figures to share yet and I've not tried precipitating anything from the butyl acetate using citric or any other organic acid so sharing this is very preliminary.

The main question is, have any of you tried dissolving precipitated harmala freebase in EA? If so, does it dissolve only slowly? Or maybe butyl acetate is simply a worse solvent for these compounds? This latter point would kind of help if it turned out that, say, harmine was far more soluble in BA than harmaline was. Alternative routes to a goal can be helpful (as this thread nicely illustrates :) )
 
Hey DFZ,
EA is obviously good at extracting fb harmala but when it comes to dissolving pure freebase harmala it can take a bit of shaking and is alot easier with warm/ hot EA.

I hope that helps answer your question. Maybe try warm/ hot BA and a bit of shaking.
 
Thanks, that's more or less what my next steps will be. I'll stick a test tube in a warm ultrasound bath.

Any idea if EA shows a significant solubility difference between H/DHH/THH?
 
Small update: something but not everything of a 60mg (well, 0.06g) sample dissolved with warmth and ultrasound, forming a faintly pink solution in 4mL of BuOAc. On standing for several days, the pink colour has intensified, very much in reminiscence of harmala red. So, oxidation appears to be occurring since the rate of evaporation of solvent is less than the increase in colour intensity.

As far as adding citric acid goes, I've been busy on numerous other things [including the actual grunt work of a standard water-based harmala extraction which kind of leaves me wishing I had the ethyl acetate available 😁] Butyl acetate doesn't entirely look like it comes up with the goods on this one. Still, in the next day or two I'll pull the liquid off, weigh the residue, and see what crashes from the actually rather lovely salmon pink solution with a sprinkle of citric.

After getting some purified alkaloids from the aqueous shenanigans, I'll have another pop at some solubility measurements using the different alkaloid fractions and a larger volume of solvent. I still have some hope that BuOAc will at least be selective for one or other of the components, which ultimately might prove somewhat useful.
 
OK, here's an update: I finally filtered the test solution. It went from pink to orange - but then it went back to pink again?! Maybe it was the lighting - but I'm sure I checked all of this in daylight. Maybe it was just telling me to hurry up before it turned green...

Anyhow, from 0.06g being treated with 4mL BuOAc, 0.05 g of solid was recovered after washing with a further 1mL BuOAc. The solution after filtering was still a lovely deep pink colour.

It was just about possible to dissolve 0.02g citric acid in 2mL BuOAc after shaking the BuOAc with a little distilled water to wet it. On adding the citric acid solution to the pink extract, a thick, milky precipitate was formed immediately and the colour changed to sunshine yellow.

The precipitate has been settling very slowly for about 24 hrs so I'll get back about that when there's something to test. Hopefully it's not just quinazolines :lol:

I'll soon have a huge pile of various harmalas to play with and we'll see what happens with things at bigger than the test tube scale. Certainly I want to put some better figures on it and my present, crappy scale is almost wholly uninformative for quantification at less than a decigram. Fortunately, the Missus agrees that a good balance would be a sound investment.

_Trip_ said:
Quick question does your country not sell acetone free nail polish remover?
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It's not something I ever thought of looking for but thanks for the tip! I could in principle find EA online but I'm an OTC kind of guy.
[EDIT: so they have some on special offer at the local drugstore 89ct. for 200mL but of course it's full of fragrance and also has a dash of ethanol added, just to be annoying. There's another one at the other drugstore which is around twice the price but without the alcohol and, amusingly perhaps, with added butyl acetate instead. Fractional distillation is fun of course but separating ethanol from ethyl acetate is exceedingly difficult. I might have to thermolyse acetone into ketene :shock: and bubble that through the mix.]
 
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