1kg Syrian rue extraction

[intosamadhi]

So, I have a supplier in India who I manage to pickup my rue from for $11 per kilo. So I figured I'd go big and try a 1kg rue extraction.

First phase was to grind and cook 1kg of seeds in a large pot, simmering for around 1 hr.

Phase 2 was to acid wash the resulting mix over the course of several days, by adding about 1 litre of boiling water plus vinegar, waiting for it to cool and then sucking off the liquid, leaving behind the seed mush.

Must've used over 20 litres of water. I used 2 large 5 litre glass containers. 1 for seed mush and the other for storing the sucked liquid. Once the storage container was fullish I reduced it over the stove and carried on adding more to it. A lot of silt settled to the bottom which was eventually added back to the original mix. It was laborious work. I eventually stopped sucking off when the liquid started looking pale yellow and if left to settle became mostly clear.

Phase 3 was to reduce the final liquid to a manageable quantity. I eventually ended up with what looked like just under a litre of thick red syrup.

At this point I wasn't sure how to proceed. Freebase or manske. In the past when working with smaller quantities I have done a manske here, and freebasing after always worked well. But this time because the syrup was so thick, when I added the salt, the whole mix became a thick sludge. No way of separating out the harmalas with that. I added a bit more water, but still, at least 80% of the mix looked like sludge. I separated a bit of the sludge, dissolved in vinegar and water and then added sodium carb. Now this mix has some whitish material settled at the bottom, a darker layer above that and then a yellowish brown liquid above that. I figured this might work for the rest of mix. So I added more vinegar and water, warmed it up and then left it to sit.

Now i am in a bit of a pickle. The mix has separated into 2 layers. A reddish liquid and lot of brown sediment. But I can't figure out where the magic is. Its possible that because I added around 200g of salt to less than 1 litre of syrup in the beginning that even after warming it up again and adding more vinegar and water that once it cooled the harmalas again crashed out. Or it's possible that the sediment is impurity and the magic is in the red liquid.

I've attached pics of the process. If anyone has any bright ideas of where I should go from here I am all ears.

 

[tryptographer]

If it's acidic and saturated with salt/chloride, the goodies must be in the precipitate.

I think you over-concentrated the liquid... when scaling up you just have to deal with larger volumes than usual

Filter, re-dissolve the residue in distilled water, basify. There sould be a precipitate: freebase harmalas. Let it settle, wash, decant, repeat a few times... my two cents.

Don't throw anything away, test the filtrate too, good luck!

 

[obliguhl]

No, your harmalas are the sediment. The thing is, if you are working with larger quantities, it is easy to crash out the salts too quickly which leaves a very impure product and kind of defies the whole thing. Use less salt or a less concentrated solution - harmala hcl should slooowly crystalize . Don't put it in the fridge immediatly, rather let it cool at room temp first. Then, if your container is cool to the touch, stick it in the fridge, but chances are, most alks are already out of the solution by then.

The result should a thick, fluffy, golden batch of crystals with no visual liquid left. If you have achieved that, it is time to freebase.

tryptographer is right!

 

[ouro]

At this point I think it would be safest to separate the solids at the bottom from the liquid, then base the liquid to see if anything precips out. Combine all the solids, dissolve in warm acidic water, let it settle, filter, then manske again. If you do have some harmala hcl in there because of your first manske attempt, remember that is is barely soluble in cold water.

For future reference, after making tea its usually much easier to just base it and precip the freebase instead of reducing. The crude precip can be easily collected and redissolved in a small amount of acidic water. Reducing raw rue tea is the cause of most of the headache when extracting and can be avoided very simply in this fashion.

 

[intosamadhi]

Thanks for the advice guys! I am separating the liquid from the sediment. To freebase the solids do I need to first warm them up with more vinegar or will sodium carb be good enough to base the harmala hcl? Or does it not even matter.

At this point I am not really concerned about yield.i just want something solid and small which will be easy to travel with, I have 5 days till I have to leave where I am staying. At the moment there is too much sediment so I want to try cleaning it up a bit more. I was hoping to end up with about 100g of impure freebase which will be easy to pack and cleanup later.

 

[ouro]

for simplicity and ease, you can just base everything and discard the fluid. I'm not sure if basing the liquid will dissolve the harmala hcl crystals and then precip freebase. You may want to dissolve the harmala hcl in warm water first, or if you manage to isolate them just wash them in ice cold water - keep the clean harmala hcl as a product.

If you base, you can wash this precip a few times with water and it will serve fine as a crude extract. Later, you can further purify it by successive acidify -> filter out solids -> base -> remove liquid iterations and/or a manske. Manske is by no means necessary for most people. IMO the further purification steps are only really useful for removing the rue taste. When its well purified the freebase is basically tasteless.

 

[intosamadhi]

Update: So i sucked off as much of the liquid as possible and then added warm water to the remaining sediment. I then based with sodium carb and calcium hydroxide. I am running out of sodium carb, so i thought mixing with calcium hydroxide to create a weak NAOH solution would be best (I am still in india so it's not easy to come by decent chems, especially where i am right now). I got it up to ph 10, is that good enough?

So now it looks like the freebase is crashing out. I have saved the liquid in another container, was waiting to see if anything else would crash out of that, in case some harmala hcl got dissolved in it, but nothing so far. I am too weary of mixing it with the rest of the solution to basify, in case something else goes wrong (like i run out of base). Also since it would seem that the manske worked at isolating the harmaline and harmine, what i have left should be free from the other rue alkaloids, and should be more usable even in its impure form, correct ? With the liquid i have set aside, would it be wise to try and manske this again and just collect whatever precipitates ? Then if anything does drop out I can use the little base i have left to fb that.

Finding a way to dry out the end result is going to be my next nightmare.

What form does harmaline acetate reduce to? Solid, resin, or goo ? My idea here is, instead of drying out the fb once i've cleaned it up, instead to acidify again and then reduce over heat. If its goo, then i would just combine with tumeric until it becomes a dry paste. but if its resin and it sticks to the pot, then that is too much hassle. Perhaps instead i could just combine the wet freebase with tumeric to create a dryish paste. Its almost winter here now, so not enough heat inside or out to dry it. I thought of laying it out in a baking tray and then hovering it over some tea light candles to slowly warm and dry it out. Comments?

Am i winning?

 

[obliguhl]

Why don't you just put it in a coffee filter, squeeze all the liquid out and then flatten out the paste to dry? I've used a blowdryer in the past with great success. I don't see why this has to become a "nightmare" at all.

 

[intosamadhi]

No coffee filters here :-( also theres way too much in there to try and filter, it looks like its over 250ml volume of dirty freebase, even with cleaning I don't think I will shrink that down significantly. From 1kg I should end up with between 30-70g of clean freebase right?

a blow dryer sounds like it might work.

 

[ouro]

You could pour it into a pan and dry it above a refrigerator or hot water heater or AC unit etc. It sounds like you might need to get creative. What else can you use as a filter? if you run short on time just use some cloth and accept your losses. If you have access to epsom salts and an oven you can dry them and make a makeshift dehydration chamber. Once whatever you've got is fairly dry you could just flood it with dry epsom salts and mix it around to make it handlable. The volume will increase but it might be easier to move and you can wash the epsom salts out later.

at least you could pour most of the liquid with some of the precip off into a tall, thin container and let it separate and decant.

I don't think I ever dried out harmala acetates but I'd bet on them being goopy and nasty.

I hope you are familiar with where you are going and feel comfortable traveling with 50-100 g of grey powder, which could be very inconveniently misidentified.

 

[tryptographer]

No coffee filters, hard to get bases... but blow driers no problem :shock:
I hope this will boost your improvisation skills! Filtering is one of the most important separation methods in chemistry, especially when working with harmala extraction.

Think before you start with such huge batches!

Hard to tell from here, there may be anything in the sediment by now: calcium carbonate, undissolved calcium hydroxide, salt, and last but not least: harmala freebase
No reason to panic: if you manage to filter it or even decant the liquid it should be OK.

 

[intosamadhi]

Yeah, I realised I would be creating calcium carb when I did it but figured that since its benign and I will only be using this for oral or nasal admin that it would be fine. The other stuff is coming out in the washes. Its looking good at the moment so I am still hopeful. Any ideas on how to remove the calcium carb if I try to refine later? Re dissolve in vinegar and manske again? Acetone?

 

[intosamadhi]

Actually filtering hasn't been such a problem because of all the decanting I've been doing. I only had to filter the fine sediment through cheese cloth before reducing the tea.

I didn't go into this blind since I've done a couple successful extractions on smaller quantities. Doing a big batch changes some of the parameters though. But if this is successful I won't need to extract again for a year or two and if not then I just lost $11 :d

 

[tryptographer]

Actually filtering hasn't been such a problem because of all the decanting I've been doing. I only had to filter the fine sediment through cheese cloth before reducing the tea.

I didn't go into this blind since I've done a couple successful extractions on smaller quantities. Doing a big batch changes some of the parameters though. But if this is successful I won't need to extract again for a year or two and if not then I just lost $11 :d

Sorry if I sounded a bit disrespectful about the 'thinking' part!

Yes, the calcium carbonate will easily dissolve in vinegar or HCl if you do another Manske with the correct concentrations. With such a large volume cooling slowly you should get nice large crystals. I hope to see a picture of a huge cake of golden silky crystals soon, good luck!

 

[intosamadhi]

Sorry if I sounded a bit disrespectful about the 'thinking' part!

No worries, my questions do make it sound like i've never done it before. I knew it was risky when I started but 'nothing ventured, nothing gained'.

I'm giving the mix one last wash right now before I attempt drying. It's not as clean as I would like, the rinse still has a bit of color to it, but its mostly clear. I've saved the water from the first 2 washes and have had lots more dropping out of that, but now i am running out of time and containers! It's interesting to see the mix of shades in the precipitate. I'm assuming that the cream colored speckles are the good stuff and the darker ones are silt from the original tea. I think the small white layer at the very bottom must be the calcium carbonate. The pics make the water look a bit darker than it is. When i suck it out with the baster its a clear yellowish liquid though. I suppose the sheer volume of it is adding to the overall color in the pics.

 

[DreaMTripper]

Nice work but I dont envy you having to decant those! When I did it everytime I put the turkey baster in it to suck out the liquid it disturbed the bottom layer of hamalas and dispersed them throughout the jar, very frustrating!

 

[intosamadhi]

Nice work but I dont envy you having to decant those! When I did it everytime I put the turkey baster in it to suck out the liquid it disturbed the bottom layer of hamalas and dispersed them throughout the jar, very frustrating!

Ya, I found the trick is to never get too close to the bottom till the end, with jars this size the end is veeeerrrrryyyy far away. Has taken me hours of sucking. When you do get to your last wash, just tilt the container very carefully so that you have a deeper end to suck from. I never get all the water out though, only when drying

 

[intosamadhi]

So now i am attempting to dry. I have a baking tray full of freebase mud. I've suck off as much liquid as i can using a tiny 3ml syringe. Tried using the hair dryer, but it's too slow for such a quantity. I would have to sit over it for hours and end up frying the dryer. So now i have resorted to hovering it over some tea light candles.

If anyone has a simple intelligent solution for this i am all ears. I don't have anything else to warm it on, and am worried that excessive heat will kill the magic. How much heat can fb harmala's take ? I have a gas stove but thats about it. It might work to dry it out in portions, spreading it thin over a plate and then using the hair dryer. But again, there's so much of it that it will take days. I may just have to bottle up the mud and travel with that.

What do you guys think, better to keep drying or reacidify and then reduce that to something solid?

On the positive side when it does dry it is a beautiful cream coloured powder. It's the cleanest I've ever gotten it before.

 

[DreaMTripper]

Harmala vapourize at around the 150 mark iirc? So maybe a double water boiler set-up? You cant just go to bed and leave it though, obviously being a gas stove.
You may have to resort to multiple coffee filtering which loses a great deal of alks, then just dry the filters on a double boiler set up.

 

[intosamadhi]

The solution was right above me. The air here is very dry so I spooned most of the mud into a smaller jar to let gravity separate more of the water. I spread a thin layer out on the baking tray and then left it under a ceiling fan all night. By morning it had dried sufficiently. So far I've collected 16g and that's only a tiny fraction of it all. I know it's not super pure but if I dry 100g and that gets reduced to 50g with extra cleaning up it will still be a great success. Gonna get some more plates so I can spread out more and dry the rest!