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Purification after manske

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Loveall

Loveall

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While it is easy to get crude harmalas, cleaning them up (for whatever reason) is not that trivial.

Not sure if this has been discussed before:

- After the first manske (fridge rest precipitation) one has brownish (dirty) xtals
- Instead of (the standard) filtering and recovery of the dirty xtals, heat the solution to boiling (water bath or microwave)
- Harmala HCl dissolves in hot salt water, but a lot of gunk does not
- Filter the hot manske solution. The harmal HCl goes through the filter while the gunk remains behind
- Minimize losses: Using ~18% NaCl hot water (near boiling) extract the (slightly sparkly) gunk left in the filter/jar ~3x (100ml at a time if starting with 5g of crude harmalas). This can be combined with the first hot salt solution and cooled (or kept separately to keep track of the extraction amounts).

Interestingly, this indicates the gunk that precipitated during manske does not dissolve in hot salt water, while harmala HCl does. This allows for a nice separation I believe. See image belows for what is left in the filter and what xtalizes after filtered hot solution is cooled. Never got such clean xtals this "early" in the water extraction process.

Bott lime: The hot salt water filtered extracts xtalize clean looking yellow xtals while leaving behind brown gunk.

Sharing since it seems like a way to purify harmalas. Not sure if this is already known or discussed, I don't see it as an option in the current TEKs (which are admittedly a little old).
 

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Great that extraction and purification of harmalas is still evolving!

Will try, perhaps it will make separation of harmaline / harmine better.
 
Awesome, the thing that always got me with harmala extractions (and in particular causing me to give up in disgust) was the intractable sludge that seems to keep on appearing from nowhere. Do we even know what the sludge is? Flavonoids, maybe? Pectin? Condensed polyphenols? Oxidation products of harmol, harmalol or one of the quinazolines or hybrid alkaloids? A combination of any or all of these, plus more?

Whatever it is there seems to be a lot of it and it keeps on congealing, so if this is a rapid way of getting rid of lots of it, and in such a simple way too - well, hats off to you once again, Loveall!

For the hot filtration, did you use anything like a steam bath to keep things hot while they were in the filter?


Murklan - that's a good point; it would be good to see how it affects the separation process. The sludgy stuff could possibly act as a buffer which would potentially make pH control more tedious (in terms of getting good, sharp changes in pH) and consequently smear out the precipitation range.
 
No hot steam bath. Unfortunately some harmalas precipitate towards the end of the filtering step (even though it is fast, it cools down enough). Hence the need for 3x hot salt water pulls of the sludge, after wich the sludge loses its sparkle.

I dissolved the resulting harmala HCl (after cooling and xtalizing in fridge) in water and crashed with ammonia. I'm seeing large white free base harmala needles for the first time (usually, I get a powdery tan product). The image below is for free base harmalas.

Reason I'm interested in purity is because I plan to try use this product is e-juice/vaping.
 

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Try a defat with limonene. Discover an entirely different Rue extraction process. So clean, the base before the first manske has no effect whatsoever so can skip straight to first manske after filtering. So obvious and yet so overlooked. Will write up a new tek shortly. Have just seen result of first manske from testing the defat idea. The surprise is only one defat required. Iwas sure reductions etc would require additional defats. They do not. Happy days :)
 
That's interesting tripwire are you saying you end up with cleaner crystals? How are your yields?

I don't know if this information helps either Loveall but I almost get an opposite effect with the EA approach for harmala. I've switched to heated EA and have been getting better yields and still nice greyish white FB crystals but upon redissolving the FB in EA (if say I was to convert it to citrate crystals later on) even if heated I'm struggling to get it all to dissolve at times and end up with some sludge that won't redissolve in hot EA. I'm thinking this could be a saturation issue and maybe not enough EA. But it has me intrigued that initially it pulls fine but when trying to convert the end result FB later on some stuff is left behind. Not sure it's a purity issue as 200mg is great for full MAO inhibition.

Either way thanks for sharing.
 
I deal with this black/brown sludge before manskeing.
Acid cook -> base/filter -> acid -> filter and you get all this gunk out.
From there you either base to recover the full spectrum or a single cold manske step already yields clear golden crystals.
 
ShadedSelf said:
I deal with this black/brown sludge before manskeing.
Acid cook -> base/filter -> acid -> filter and you get all this gunk out.
From there you either base to recover the full spectrum or a single cold manske step already yields clear golden crystals.
Click to expand...

I do get some gunk out after the second acid step (stuff that doesn't dissolve again), but the resulting manske xtals are red/brown.

What bases and acids are you using? pH targets? Do you dry the product in between any of these steps? Any other details you can share (e.g. how you extract the seeds initially)?

Thanks!
 
I do get some gunk out after the second acid step (stuff that doesn't dissolve again), but the resulting manske xtals are red/brown.

What bases and acids are you using? pH targets? Do you dry the product in between any of these steps? Any other details you can share (e.g. how you extract the seeds initially)?

Thanks!
Click to expand...

I use vinegar and NaOH.

Procedure:
Boil seeds in water with some vinegar, dont reduce, I do multiple runs instead with the same seeds, base each run individually, filter and wash, dissolve freebased alkaloids with vinegar in the same filter, here is where all the gunk stays, usually this is enough but sometimes the solution is not completely clear and I pass it through a finer filter.
From here either final base or redissolve in vinegar and cold manske.

I add base until the solution stops shining cyan under a 365nm uv light and becomes pure, vibrant green, ph is around 11, going beyond this point makes the green fluorescence more and more pale, but nothing seems to precipitate.

First base, akaloids start to precipitate as pure milky white and quickly become more and more brown as they crystalize further and probably trap some impurities, you can see a darker line in the top precipitate as impurities mix with the crystals.
Second base to retrieve full spectrum, alkaloids stay whiter, they still turn slightly off white, there might be some impurities in there still, though it could also be Harmine since it seems to crystalize in brown shades depending on the conditions(??).

My theory, I feel like this brown sludge is made of very fine particles and they will show up in whatever step you let them time to "aggregate", this could explain why cold maske stays golden while the hot one will get slightly browner/redder even if the parent solution is the same.
 
_Trip_ said:
That's interesting tripwire are you saying you end up with cleaner crystals? How are your yields?
Click to expand...

I am currently evaluating this idea. The early signs are incredible. Since we have some rue specialists in the locality, I implore to you all, use your intuitions! Have you not noticed the little puddles on top of your solutions and how it inhibits crystal growth? Have you not wondered just why the rue is so difficult to filter? Did you not pay attention and notice what changed over the many iterations towards perfection. And above all else, did you not notice that the surface of your final manske solution was at last devoid of colourful but oil slicks?

Instead of being proud for discovering this defat game changer, I actually feel somewhat embarrassed for not having figured it out sooner. It's been staring me and all of us in the face through every difficult part of this extraction for years!

May I further suggest that it might just be the case that any extraction from plant material might also require a trivial defat before filtering is attempted? What can be lost from the solution in acidic phase? What can be gained from trying? It's a no brainer guys...
 
tripwire - Have you tried defatting with solvents other than limonene?

On the basis of residual fluorescence, I think harm(al)ine citrate might be very slightly soluble in n-butyl acetate but that's likely a trivial concern in comparison with what appears to be a significant benefit in doing the defat.
 
downwardsfromzero said:
tripwire - Have you tried defatting with solvents other than limonene?

On the basis of residual fluorescence, I think harm(al)ine citrate might be very slightly soluble in n-butyl acetate but that's likely a trivial concern in comparison with what appears to be a significant benefit in doing the defat.
Click to expand...

No. Limonene seemed to work perfectly and is the only wide spectrum non-polar solvent I have. I have complicated the technique evaluation by introducing some slight oily contamination, which set things back a manske or two. I have just set the 4th manske in motion which is looking promising. When dissolving the alkaloids for this attempt I put them under solubility pressure and a huge amount of muck got isolated. Finally got the crystal clear red liquid desired. Still something on the surface but I have pushed the minimum solvent limit a bit more than usual so could just be forced early precip.

Very small amounts of contamination can have significant results with rue. While I clearly have most of the alkaloids from the first two pulls, I have the third in the pipeline and will not make the mistakes i made this round, in order to fully evaluate the defat, and it seems, minimal solvent purification technique that made itself manifest tonight.

If I see evidence of oils in the solution currently manske-ing then I might just go for a second defat and re-manske. I'm a bit cautious given how loaded the aqueous fraction is, but if it works when much more dilute, there should maybe be no reason why it should fail just because highly concentrated and ultra pure?
 
_Trip_ said:
That's interesting tripwire are you saying you end up with cleaner crystals? How are your yields?

I don't know if this information helps either Loveall but I almost get an opposite effect with the EA approach for harmala. I've switched to heated EA and have been getting better yields and still nice greyish white FB crystals but upon redissolving the FB in EA (if say I was to convert it to citrate crystals later on) even if heated I'm struggling to get it all to dissolve at times and end up with some sludge that won't redissolve in hot EA. I'm thinking this could be a saturation issue and maybe not enough EA. But it has me intrigued that initially it pulls fine but when trying to convert the end result FB later on some stuff is left behind. Not sure it's a purity issue as 200mg is great for full MAO inhibition.

Either way thanks for sharing.
Click to expand...

Maybe it is a contaminant that denatures when dried from EA? After denaturing it does not dissolve again? Just a thought/possibility.
 
Heya @tripwire and @Loveall , wanted to ask for your final results. As i am preparing for my first harmala extraction from the rue seeds and looking for the easiest/updated and most efficient one. Can you share some of your result on how do you perform rue extraction this day? Possible with easy to understand recipe? Thanx.
 
_Trip_ said:
I believe it is here

Harmala extraction - unneccessary steps?

Harmala extraction always includes the step of precipitating Harmala*HCl as a purification stepnamed after Alkaloid-Chemist Richard Manske. During my first Harmala extraction I totally failed at it, as the resulting crystals were way too fine to filter so it was not doing anything. I even tried...
forum.dmt-nexus.me forum.dmt-nexus.me
Click to expand...
My sweet Lord. No filtration required? This seems to be so so easy way...
 
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