Manske extraction

[Indole]

Anyone have any success with this method used during Syrian rue extractions? I have tried it several times with lackluster results. How necessary is it even to remove the unwanted alkaloids?

Sorry of I posted this in the wrong forum, mods please move if this is the case.

 

[skillet]

Yeah, I tried to get pure harmine by basifying with ammonia, but without a microscope or even a magnifying glass I'm not sure how well it worked. I don't think it's really necessary to remove the harmaline and whatever else, just wanted to try it. It's pretty easy to get the mixture of harmala alkaloids though.

What did you try and do exactly, and what/where was the problem?

 

[Solipsis]

Just for the record, I am not seeing a 'synthesis discussion' problem here for all crew and users wondering. For now, at least.

 

[sekio]

The extraction is detailed here for those confused like me.

 

[Indole]

Thanks Solipsis for the stamp of approval. As far as I know, this process is completely legal in the united states, as are the harmala alkaloids.

Skillet, I am not trying to separate harmine from harmaline. I am trying to get rid of unwanted alkaloids like vasicine and vasicinone by taking advantage of the harmala alkaloids insolubility in NaCl saturated water.

I have tried two methods, for both i started with harmala freebase (previously extracted from syrian rue seeds.)

1st method: I dissolved the freebase alkaloids in hot vinegar and then added 10g NaCl for every 100ml of solution. As soon as I finished adding the salt the alkaloids were already crashing out, but were not making nice long crystals as I was expecting. However, I suspect this was because I did not filter enough. I have since filtered thoroughly.

2nd method: Again, dissolve the freebase in hot vinegar and add to it an equal volume of NaCl saturated water. This solution was allowed to cool slowly, and sat overnight in the fridge. But no crystals formed.

At this point I have a nice looking solution of harmala alkaloids in aqueous HCl. It has been filtered many times and is a deep red which glows under blacklight. I could post pics if requested.

So any advice on how to get this to work? For reference, I got the "tek" from the nexus.

 

[sekio]

Try concentrating your solutions down, the crystals will ppt out then.

 

[Indole]

Well I don't want to boil the water off and concentrate the solution down because I am working with HCl and I don't have the luxury of a fume hood.

 

[dg420]

Well I don't want to boil the water off and concentrate the solution down because I am working with HCl and I don't have the luxury of a fume hood.

thats only an issue if there was a huge excess of acid used, when did you add hydrochloric acid? the ingredients listed were salt and acetic acid, right?

you found this method at nexus, have you asked there?

 

[Indole]

I wouldn't say a huge excess was used, I used the HCl because using the vinegar requires working with a larger volume of liquid because the vinegar is only 5%. More liquid is cumbersome and something I want to avoid. Boiling the water off would probably liberate some HCl as well, and that's not really something I want lingering around my kitchen.

I have not asked at the nexus. I don't have an account, nor do I trust the feedback as much.

Here are some pictures:

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^Solution of harmala alkaloids in 400 ml aqueous HCl

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^Different angle, same as above.

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^After heating and addition of 150g NaCl. You can see the haramalas falling out as those yellow flakes, and a layer of salt on the bottom, indicating that the solution is fully saturated.

I am going to let this solution sit, chill, and separate for a while, then decant off the water, try and filter the harmalas, and wash the salt out. Maybe heating up the solution more would have produced the long, spectacular crystals seen in the nexus teks.

 

[skillet]

Yeah a proper filtering is essential, it sucks to do it with coffee filters.

Your third pic looks good, I wouldn't expect great crystals from the first crystallisation. I'm not sure mine looked as nice as that. If you filter it, wash it with saturated salt solution (don't try and wash the salt out, you'll probably lose a lot) and crystallise again you should get some nice needles. The way I did it was to dissolve in some hot water (about 200mL for just over half a gram), saturate it with salt, and gradually dilute it with more hot water (all the while keeping it almost boiling in a pan of water) until everything just dissolves. Then take it out and leave to cool slowly. The final salt concentration was probably around 25%, I'm not sure 10% is enough, maybe if your alkaloid solution is more concentrated.

To get the HCl salt uncontaminated with NaCl I made a slurry of the freebase in a little water and added concentrated HCl slowly until it all dissolved, then just threw in a load of hot acetone, put it in the freezer for a while, filter, wash with acetone:

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[Indole]

Thanks for your advice skillet. As far as filtering goes, I had success with plugging the bottom of a funnel with cotton balls and letting the liquid run through.

To get the HCl salt uncontaminated with NaCl I made a slurry of the freebase in a little water and added concentrated HCl slowly until it all dissolved, then just threw in a load of hot acetone, put it in the freezer for a while, filter, wash with acetone:

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You think you could explain the chemistry you used here? Does the addition of acetone push the HCl salts out of solution at cold temperatures? I'm not a noob so feel free to go into detail.

Here are some new pics:

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^After a night of settling out in the fridge.

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^After decanting. The yellow sludge is the HCl salt.

I had another idea on how to isolate the freebase, but I'm not sure if it'll work. I was thinking about redissolving the HCl salts in distilled water until everything is completely dissolved. Then a defat will be performed using a small amount of xylene. Then the solution is basified and freebase harmalas fall out of solution. The freebase is then extracted with xylene (or another solvent) and the xylene is evaporated off to leave the freebase crystals.

Is this method worth it? Will it even work? I guess it depends on the solubility of the harmala freebases in xylene, but judging by their structures they should be pretty soluble, no? If not, do you have any other solvents you might recommend? Thanks.

 

[skillet]

Thanks for your advice skillet. As far as filtering goes, I had success with plugging the bottom of a funnel with cotton balls and letting the liquid run through.

Really? How did you get the freebase though, A/B extraction?

I just extracted the seeds with vinegar, strained them out and put the stuff in a 2L bottle, plugged the neck tight with cotton, poked a few holes through the cap and screwed it back on to keep the cotton in. Then sat squeezing it into a jar as hard as possible for 5 min, and threw away the last bit when I got tired

I found that wasn't even enough though, it still looked a little cloudy and some plant crap fell out with the harmala crystals so I had to filter it with coffee filters, went something like - pour 100mL into filter, let 50mL drip through and throw last 50mL back into the unfiltered solution, throw out coffee filter, repeat 5 or 6 times with fresh filters. After that everything worked fine though, and the next time I put it through a coffee filter (to get the crystals) it went through quick without clogging.

You think you could explain the chemistry you used here? Does the addition of acetone push the HCl salts out of solution at cold temperatures? I'm not a noob so feel free to go into detail.

It's not soluble in acetone, if you add enough (and don't use too much water) most of it'll crystallise out. Methanol might be better, but I didn't have any. It's not very soluble at all in IPA so I didn't have any luck crystallising it from that and acetone.

To make the freebase you can just dissolve the HCl salt in water and add excess ammonia or NaOH or whatever, leave it stand for a while, filter off the crystals and wash with water. You shouldn't need to defat or extract, your sludge looks pretty good already, but I guess xylene would be an ok solvent. I only tried naphtha on the freebase, and it's only slightly soluble in that.

 

[Indole]

Yes I got the freebase through acid base extraction. I have converted between harmala salts and harmala freebase many times so far trying to figure this whole extraction out.

That's a good method you have there with the 2L bottle. I might have to try that next time

I managed to filter my harmala HCl, salt saturated solution through coffee filters and managed to get almost all of the yellow crystals. The crystals are drying now and I will update with pics soon.

I like the idea of using acetone to precipitate crystals. So here's what I'm thinking: dissolve the harmala HCl crystals in a minimal amount of hot, distilled water. Add acetone. Put in the freezer. Wait. Filter the solution through a coffee filter, and collect the solids. This would theoretically leave me with pure harmala HCl crystals without an excess of HCl, allowing me to eat it safely.

Do you recommend converting to freebasse (for whatever reason) or could I just stick with the salt?

Oh, and I tried dissolving a small amount of freebase (left over from an earlier part of the extraction) in an excess of xylene, and it is definitely not soluble in xylene. So scratch that.

 

[skillet]

I have converted between harmala salts and harmala freebase many times so far trying to figure this whole extraction out.

Yeah me too

I like the idea of using acetone to precipitate crystals. So here's what I'm thinking: dissolve the harmala HCl crystals in a minimal amount of hot, distilled water. Add acetone. Put in the freezer. Wait. Filter the solution through a coffee filter, and collect the solids. This would theoretically leave me with pure harmala HCl crystals without an excess of HCl, allowing me to eat it safely.

Yeah but harmala.HCl and salt, unless you convert it to the freebase first and make the salt with hydrochloric acid. That's the main reason I freebased it, that and I thought I might be able to recrystallise the freebase as an additional stage of purification... So I'm storing it as the HCl because it's probably more stable, and just freebase bits as needed for playing with changa.

Oh, and I tried dissolving a small amount of freebase (left over from an earlier part of the extraction) in an excess of xylene, and it is definitely not soluble in xylene. So scratch that.

Oh ok, what solvent did you use for the A/B then? And how about hot xylene?

 

[Indole]

I didn't use a solvent for the A/B, I just had some crude freebase harmaloids on a filter paper from a botched filtration attempt. And I tried hot xylene: no dice.

Here are some pics:

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^Harmala HCl crystals with some salt impurities. I haven't weighed it yet, but I will before I recrystallize it.

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^On the right is a dilute solution of harmaloids, and on the left is a more concentrated solution. Cool right?

I am planning on dissolving the salts in hot distilled water, filtering, adding acetone, and freezing. Hopefully this will give me pure Harmala HCl.

 

[Indole]

I never updated this with final results!

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^Pure Harmala-HCl salts that are very fluffy and crystalline. I got this from the salt-contaminated product above by redissolving it in an acidic, aqueous solution, adding salt, and letting the solution sit for days at about 45-60 degrees Fahrenheit. After several days I checked on the solution and found large snow-flake-like harmala-HCl crystals floating around in the solution. Very cool.

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^Same stuff, different angle. There is about .25 grams here I think. I lost a lot of product throughout the extraction due to first-time errors, and general fuck-ups. Next time I should get a much higher yield.

I have yet to try this product, although I did try about 140mg of crude freebases which was most certainly an active dose!

 

[sn23]

Wow, absolutely beautiful

Did you strictly follow the Mankse recipe? Key is loads of filtering (series of consecutively tighter cotton balls and coffee filters) and patience, I think.

About 20-40 mg sublingually 15 mins before vaped DMT is considered an interesting experiment (dose the latter adequately lower).

 

[Indole]

No I didn't strictly follow any recipe, just kind of used guidelines from around the web and my own general knowledge. I didn't know Harmala-HCl was active sublingually, is there any advantage to dosing that way versus orally?

 

[sn23]

The freebases certainly are active sublingually. Around 30 mg of them sublingually enhance vaped DMT. In the sense of increased potency and duration. Advantage is the faster onset of harmala effects plus you don't need full MAO inhibition or worry about an empty stomach.