100g syrian rue extraction, tea > base > acid > base > acid then manske
i'm using distilled white vinegar as acid and strong NaOH solution as base
a reasonable amount of HCl xtals was retrieved(first pic)
so i tried to basify the leftover solution to see if it still has any harmalas and i got these cool looking blobs, they don't look or behave like freebase harmalas, are they the quinoline alkaloids?
what do you think? can i safely discard them or should i try and collect them?
i've done this before but i don't remember such results.
crashing of freebase harmalas for comparison(last pic)

Interesting.

I once basified the filtrate to recover leftover harmalas and the recovered HCl crystals from Manske step were exclusively the needle-type ones so I assumed they were mostly from haramala alkaloids.

The second run may still be worth recovery but later the crystals were so large and the filtrate so clear that recovery was not viable.

Love the blobs!

(no idea what they are, but look very cool)

I've tried very hard to recover something useful from basifying a manske filtrate, it's no use, all unworkable slime and blobs. Once it was analyzed by someone and say it was mostly harmalas but what does that help when it is completely non workable? If someone finds a way to turn it into alkaloids that can be handled I'm all ears. For now my manske filtrates go down the drain.

totally and completely consistent with my experience.
i have no idea as to how and why this happens though, chemistry is hard on me...

They are relatively pure harmalas, the consistency is just garbage, for some unknown reason. This has been discussed a few times. Here are a few threads that touch on it:

non manske precipitates

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

[Logic Check] First time manske on Syrian Rue

so they are mostly harmalas! good to know, thanks for the links snozz.
i left it for 2 days and they settled and turned into "the slime", there was golden needle crystals on the sides so maybe i didn't add enough base, i decanted then acidified, filtered and rebased, it looks much better now and settled faster, will do maybe another A/B and a manske while keeping volumes minimal.
i am thinking of boiling it maybe it helps somehow (just a feeling).
also i got 4g of freebase so there's 2g left, i still need to do a couple ob boils on the seeds
i will keep trying to save them but won't consider it a win unless i get them via a manske

Wouldn't this be mostly harmalol? It is very soluble in water because of the -OH group so it does not fall out during Manske I think. That would be consistent with the info from SnozzleBerrie in older threads where the recovered material after leftover liquid manske basification tested as harmala yet it could not be recovered with a fresh manske.

Isn't harmalol the alkaloid we mostly remove during Manske? From wikipedia, rue contains up to,

Harmine 4.3% (seed shells)
Harmaline 5.6%
Harmalol 3.9%

Everything else is <0.5%, with vasicine in a distant 4th place at 0.25%. So after a non-manske clean extract basification there should be a mix of the 3 harmalas mentioned above and traces of other alkaloids. For example in 200mg of crude freebase there would only be of the order of 10mg of vasicine, are we sure that small about of vasicine would be an issue in any way?

Sorry for the basic question, it is just that I see everywhere on the Nexus that vasicine (which is used in traditional medicine in vasaka juice and has shown no negative effects in doses up to 16mg IV when taken alone) is unwanted and there is a desire to have it removed. I never understood exactly why, so I need to ask even though this seems to be well established/accepted. Harmalol also seems to be a beneficial medicinal substance. Maybe my wikipedia info is bad? Maybe manske is just to help remove seed raw material and harmalol/vacisine are sacrificed so this seed material can be removed? Sorry if I'm missing something obvious.

Note: I'm new at rue extractions so please be sceptical of the info above. Mostly intended as pointing out possibilities and asking questions, not trying to state facts.

My (slightly foggy) recollection is that endlessness' analysis showed harmine/harmaline. I don't remember if/how much harmalol was present. Sorry I can't be of more help :/

good points Loveall, if the vasicine content is this low then these must be harmala alkaloids.
i did a manske got some long needles and a weird precipitate but they were little so i reduced it to half the volume and now i'm having a better amount of needles
so can anyone of the chemistry people confirm that harmalol won't crash out in manske?
if yes then we must recover it with base presip, would ammonia be the best choice for this?

Hey Sakkadelic. By the way, I'm a fan of squeezing the seeds, thank you so much for pointing out that technique. I owe you saving me from difficult filtering and/or decanting ground seeds. Regarding your question, I don't know why, but this is what 69ron said years ago,



And in the same thread,




If this is all true and also applies post manske (we need a chemist to help us like you said), it could also be a way to test what is left in the post manske solution. You could run a small split test on manske leftovers with both ammonia and a sodium carbonate. If ammonia does not form the large yellow clouds (or forms very few due to residuals - as I understand it manske does not pull out all the harmala/harmaline because there is some still dissolved at a small concentration which I think is why some recommend small manske volumes), then things are starting to fall in place.

I got 60g of rue freezing to test our theories in the coming week.

Plan (feedback welcome if someone has more info/insight),

1) 10% vinegar water microwave extract using Sakkadelic's squeeze method on frozen/thawed whole seeds (5x)
2) Pressure filter across 4x stacked coffee filters, optionally do one last seed extracion with the used filter tied inside a shell of fresh coffee filters which you squeeze while slowly saying saaaakkaaadeliiic under your breath .
3) Centrifuge reduced collected liquids. From experience, oils will be left atop the centrifuge tubes, see attached picture where part of the oil stuck to the centrifuge tube while pouring off. Discard what accumulates on the bottom of the tubes (called the centrigugate). Some oil will come out, there is no practical/simple way to eliminate all the oil at this point, we will get rid of it later.
4) Basify with calcium carbonate and get to pH10+ (steady state where solution stips changing colors/look and centrifuge again, this time keep the centrifuge. Ammonia cannot be used here (in theory) since we want to keep the harmamlol in the next steps.
5) Dissolve in 10% vinegar water and centrifuge agai.n. This time there will be no oils at the top of the centrifuge tubes. I think the oils in step 3 have been turned into a solid in step 4? Soap makers may have more insight?
6) Discard centrifugate. At this time liquid will be dark but clear and beautiful. As a test, centrifuge again, no solids or fats should form. We are done cleaning up the rue extract at this point from raw particulate/oil plant matter.
7) Manske using 10g of salt per 100ml of extract. Keep crystals. Optionally centrifuge to make sure you get every beet of precipitate possible (which can sometimes make it though decanting).
8 ) Let the fun begin here.
8a) Sample the leftover manske solution and basify sample with ammonia. Little or no precipitate should form from trace vacisine (0.25% in rue seeds) and harmaline/harmine that stayed in solution at low concentration during manske.
8b) Rest of manske solution gets basified with sodium carbonate. Here, more changes in color should occur (?). Any trace alkaloids from 8a) will precipitate, along with any harmalol (0.6% or more, up to 3.9% in rue?).
9) Centrifuge and collect/dry the two basified solutions from 8 ). subtract from 8a centrifugate to estimate % of harmalol. We may get nothing here...
10) Alkaloids from step 7) can be separated and converted to harmane/harmaline/THH. From step 8 ) we also have the trace alkaloids (Vacisine + others) and harmalol with the same other traces. So potentially we could be looking at a collection of 5 separate alkaloid groups!

No idea if this will work or not, but that is why we try

Note: I use a cheap $50 4000rpm centrifuge with 120ml total capacity. I recommend it for kitchen alchemy. I centrifuge acid solutions for 10min. Base solutions need more time 30m or so and you need to work quickly to pour off a clear solution since the base centrifugate is not as sticky at the bottom of the tube. I'd like to call this CARE (Centrifuge Assisted Rue Extraction). It helps me a lot because I'm a cluts and screw up decanting all the time and don't like to wait for solids to settle. I don't like to filter either.

Step 7: 10gr salt per 100 ml: chances are that a considerable amount of harmalas will not form needles that usually would form needles under a salt-saturated solution. Why choosing such a low amount of salt? It's almost a ticket for partial-manske.
A way is to keep concentration extremely high to get max needle forming.

Loveall if you want the super fastest and no-hassle easiest way to get very high rue yield, build yourself a siphon off jar, a 15$ vacuum pump (or a dirt cheap vacuum water jet) and use a pressure pot instead of squeezing the seeds:
https://www.dmt-nexus.me...&m=822711#post822711
I've been on many rue-routes, this one breaks it all
Centrifuging 100gr of seeds aint gonna be that easy I recon.

BTW, how are you going to check your theories, only one solution: lab analyze. Is that the final aim? That would sure be very cool because without that we're nowhere.

Btw here's my frustration with basified mansked filtrates:
https://www.dmt-nexus.me...&m=826497#post826497

yukk

Jees, thank you so much for the feedback and tips and all the amazing work you have done with rue. Also, thanks for the salt amount tip during manske: I'll be careful to not undersalt.

A couple questions about the pressure cooker (PC),

1) Any concerns with hydrolyzing harmine->harmol and harmaline->harmalol at high pressure/temp and low pH? Specific concern is hydrolyzing the methyl group, which has been alluded to before by pitubo. Guess the yields speak for themselves (so no major concerns), but what pH and pressure and time do you run the PC at and still have high yields?

2) If using an aluminum PC, any concerns with Al contamination when running the PC with a low pH solution (I have a cheap Al PC for my mushroom growing hobby). Stainless pressure cooker would not be an issue.

Also, thanks for the video link, love seeing those famous blue gloved hands in action

You've mentioned on other threads that you centrifuge the last manske crystals to drive salt down. What do you use as a centrifuge?

I read through the threads you posted (thanks again). This was an interesting post. One theory to explain what was observed is that if ammonia basing does not precipitate harmalol (as 69ron mentioned). Therefore, harmalol happily stays in the water, and won't get in the way of harmine/harmaline precipitation. However, in NaOH basing, harmalol will try to leave the water (but with difficulty since it is so attracted to water) and get in the way, slowing down the precipitation. This harmalol theory is also compatible with the post manske NaOH basing observation, where NaOH precipitates harmaline/harmine easily because harmalol was removed, and is now the goo in the NaOH based manske (note that if this theory is true, the first manske will not produce goo if based with ammonia assuming no NaCl interaction, or if ammonia was used during the original post extraction basing - which is testable).

Another test for this theory would be to measure the yield on a 50/50 split extract treating each side of the split with NaOH basing/filtering/drying vs Ammonia basing/filtering/drying. There should be a drop in dry measured yield with ammonia. The higher yielding NaOH precipitate would be the crude full-spectrum stuff, with harmala/harmaline forcing (after some time and work) harmalol out in non-goo form. Maybe you have done this measurement already? Unfortunately, if the NaOH full spectrum product is washed with water, harmalol may be washed away. Fortunately said wash could be tested for goo at this point with a new NaOH (or sodium carbonate) basing, with a chance for crystals since NaCl has not been introduced yet (see next comment). However, this harmalol would be NaOH (or Na2CO3) contaminated.

The isolated goo is very problematic. Maybe it is goo because of salts? I've seen crude salvinorin extract turn to goo in the presence of NaCl salt while trying to remove chlorophyll with salt water. I can't explain why salt would gooefy anything, just an observation (and it may be totally unrelated to our situation here).

Finally, you make an excellent point about the final evidence for harmalol. You are right that we would need outside confirmation. For now, we can see if the goo continues to behave like expected under the harmalol hypothesis. If so, we may be able to crystalize it if we put our minds together (it is supposed to be a "tumeric yellow" crystal, maybe with 99% IPA which may help clean out the salt after drying?). I've attached a paper where some folks show some Rue TLC results so we could repeat that also if we get to that point. Beyond that we need a lab sample of harmalol as a TLC standard or to send the samples out. But I think there is fun work to be done before we get there.

PS: I use hop nylon bags, made for extracting hops during Homebrew. No seeds get to the centrifuge. Sorry that I did no mention that earlier.
PPS: Another interesting test would be to run the dissolved goo in a basic solution in a PC (or microwave?) with a methylating agent and catalyst, to see if we can synthesize harmaline from harmalol. The right reagents are difficult to come by (except for DMC) and handling them is beyond my abilities, but a hail mary using methylated vitamin B12 supplements (methylcobalamin) may be worth a try - would not be the first time something is methylated with it.

Edit: Methylation is NOT recommended for the kitchen alchemist. It can be very dangerous. Thanks to pitubo for pointing this out. I will be more careful to point this out in the future.

Another observation is that in the VDS protocol, the first set of crude alkaloids (full spectrum?) is 18.953g in section 3.1. VDS keeps adding Na2CO3 to his subsequent manske filtrates and mentions there is less stuff showing up at each step (section 3.2), ending up with 48% of the initial full spectrum stuff (18.95x0.48=9.1g, I believe VDS has a typo in this section and multiplied 9.1g by 4 - the number of extractions - and mistakenly reported 36.4g). Why the large 52% "loss"? Part is impurities and non-mansked harmaline/harmine, but the removal of a few grams of harmalol alkaloids fits nicely with this loss during manske.

And one more thought, have we ever tried to convert the goo (presumably harmalol which itself looks like de-methylated harmaline?) into some kind of de-methylated THH (tetrahydroharmol)? May be worth a test one day? Simply do the Zn conversion skipping manske?

I think that is enough verbose musings and wild speculations on my part. Time to turn to experiments.

i haven't tried the PC method yet since i didn't have a PC but it seems to be the best method and SnozzleBerry, Jeez and others got great results with it... now that i have a PC i definitely will be doing it from now on.
like Jees said add more salt
post manske freebase settles much faster than pre manske freebase so yeah there's something here, i personally feel it is the harmalol like Loveall is theorizing and i'd love that we catch it somehow..
i don't have anything to add i am still not at the level of kitchen chemistry.
thank you Loveall and all for your work and good luck

Maybe that pressure treatment formed more harmalol indeed, I've no idea TBH. I did have an incredible amount of that slime and 1 factor for sure was the many many washes that I did. That workflow goes so fast and easy that it is very tempting to do more, I estimated 8 or 9 washes. The last washes clearly started to precip less crystals and visibly more slimey under basing, compared to the first washes that were only crystals. It is possible that my last 3 washes not really contributed to much harmine/harmaline and that I was merely preciping/collecting the slime-harmalas. One thing stands out: no suffer on harmine/harmaline yield, so I expect (guess) that I wasn't really converting desirables into 'that slime', or at least not to relevant degree.

Time in the pressure pot: my aim was to just give time enough to get water pressed into the seeds (the decompression is then to get that water out of the seeds). This method mimics boiling/squeezing but without hassle. So for the first boil I estimated 1 hour cook, and the last 30 minutes as the seeds become mush later on. I just guessed times, pH always aimed between 2 and 3. I love phosphoric acid for this, no smell, food safe as we're on the same level of a coca cola here (pH 2.8 same acid).

I did not always took the liquid away after a boil. Often after the decompression I left it an hour and started another 30 minutes cook pressure swing, or 2. Then taking the liquid out. I dreamed of having water in and out of the seeds few times, then took the liquid out for cooling and basing. So for say 8 washes that might have been 16 to 20 pressure swings. It's a method to do less decants and still do 2 to 3 times more pressure swings. I dunno if any helped, I just did it intuitively.

It is generally known for not brewing ayahuasca in aluminum pots. The reasons should be same for brewing rue imho.


It's actually a fruit/vegetables juice/pulp separator. I stick the coffee filter well in the side so it doesn't hit the translucent carrots-guide (of the top section) when spinning. See picture.

I've never had an explanation but this one sounds viable, here again only analysis could reveal correctness of the theory.

Oh yes and is why I don't bother anymore about it, just called it a day with that slime

If it is harmalol, and if the reaction goes as planned. On practical terms if I have 6% freebase result from rue seeds without all that potential recuperating out of the slime, I settle for that 6%. But I understand your endeavoring mind. Feel free to beat the slime, I'm all ears

Thanks for the PC details Jees. I think you mentioned before seeing the pH rise during PC (or even boiling)? That could be a sign of harmine/harmaline de-methylation (?) with the -O-CH3 group being converted to -O-H by protons from the acid (pure speculation here, will try to ask a chemist in the chat). I will copy your phosphoric method instead of adding a generous amount of vinegar which could be a problematic source of de-methylating protons in the PC environment. But again, this can be tested.

That centrifuge you have looks interesting. Have you ever used it to try to get water out of the seeds? Could it complement the PC strategy?

The room in the rotating part is too small for a batch of seeds. The thing is that translucent top part has a plastic guide to aim the e.g. carrots to the rasp bottom plate. It prevents using large volumes. A coffee filter with 15 - 20 grams of extract can be nicely fitted into the side.

I think to have mentioned pH rise while filtering, during the VDS papers, but that was because the filtering act immediately removed some CO2 that was result of using carbonates on vinegar. I believe that was a 0.5 pH rise IIRC. I cant really remember another pH rise case, maybe I forgot