Help with Manske on Syrian Rue Harmalas Extraction

[brand_new_bein]

Hello, I successfully performed one stage of Harmalas extraction on 50g Syrian Rue seeds by following a mix of Gibran's caapi tek and the No Filter No Reduce tek and obtained some freebase precipitate after basing the Rue tea. I saved about half of the precipitate equalling 1.5 gram as freebase after washing it. The other precipitate i let settle in a basic mixture on which I attempted a manske to purify further as HCl salts.

So I took what I assumed to be 1.5 - 2g of Harmaals precipitate with other alkaloids and I removed as much of the basic water as I could sans a thin layer that I couldnt get rid of without loosing product. Then I added 50 mL concentrated acetic acid and about 100-200 mL near boiling water. I disloved the alkaloids into the mixture and poured it through a filter. I noticed some brownish residue in the filter which I suspected could have been undisolved harmalas so I poured some concentrated vinegar through the filter while stiring it and saved that in another jar. Then in the jar with most of the disolved filtered fluid, I measured about 250 mL solution, so I took another 200 mL super saturated salt water which was still warmish when I poured it in. Now its about 500 mL of brownish liquid in which I am expecting to see needle like crystals.

However after shaking and letting cool a bit, I notice no crystaline precipitation. Perhaps it is too early and I have put it in the fridge, but is there a chance that I have either put too much or too little of something to get precipitation? And what can I do to fix this error and obtain either harmalas freebase or salts somehow from the liquid? Should I freeze it, or boil it, or add more salt or vineger?

Thanks for your help with this.

 

[Brennendes Wasser]

In my opinion that Manske Step is not even needed. More severe it takes much more time than just settling Freebase Alkaloids for any full precipitation and then they are not easily filtered / separated.

I think the original idea was to get rid of Vasicin or Vasicinon - these carry an -OH or =O group and are therefore more water soluble - this will keep them in solution even at supersaturated situations like during Manske step.
They have a bad GHS Symbol on wikipedia, but actually that is only because they can induce premature birth at high level in pregnant women. Other than that there is absolutely no harm. And eating this stuff while being about to give birth might be a really scarce encounter :shock: .

But on top I made an analysis and found absolutely no Vasicin / Vasicinon. So either (at least in my batch) there was not any at all or they are removed anyways in the way of not doing a Manske. That would be much easier and faster:

1. Boil your seeds at pH 3 (dont grind, Alkaloids are in the shell).
2. Dont reduce and add NaOH until reaching pH 11.
3. Wait for settling of Alkaloids and then decant as much water as possible.
4. Put in a big container and fill up with more water.
5. Repeat at Step 3. until the water is completely clear or pH reaches below 8. These 2 situations will most likely happen simultaneously, so color is also just a good indicator.
6. At last decant as much as possible and fill your residual Alkaloids on a plate, evaporate in oven at 80 °C with high ventilation

= pure Harmin / Harmalin mixture, no Vasicin / Vasicinon so Manske is unnessecary work IMO. Also not even a single filter step needed!

If you dont have any precipitate you could simply start at step 2 and still get your stuff back.
Other than that there cannot be too much of anything, you could simply add more salt if only "50 % of the water was saturated" let's say.

 

[brand_new_bein]

Thanks Brennendes Wasser, appreciate all the insights you have given.

I did follow the process you described more or less and thats how I retrieved half of my alkaloids. On the other half I wanted to go this different route, in part to learn the salting procedures and possibly to end up with purer product.

I can wait a couple of days to see if nothing forms in the container. Then should I try adding more salt? If so, how much should I add without getting salt contamination? Theres a bit over 500mL of liquid in the jar now.

Otherwise, I am also happy to abandon the manske and just retrieve the freebase alkaloids. From what I understand in your instructions I can just add NaOH and get the pH high enough for the alks to crash out again. I wonder if the salt water and acetic acid water ive added in this solution wont produce something other than the original alks crashing out?

Would it be safer to just base the solution and retrieve freebase harmalas, or to add more salt to the solution and see if it precipitates any needle like crystals?

 

[merkin]

In my opinion that Manske Step is not even needed...

That is a really interesting and timesaving proposal there Brennendes Wasser!

Just a little sad because I find the growth of those golden Manske crystals so extraordinarily beautiful

But when a guy needs some harmalas el-pronto, this is well worth a try. I found Sakkadelic's method saved me heaps of time (over the Tao tek) and your method is then a refinement of even that. I have this huge 5l 'Schott' bottle (not sure what the real name for them is but almost all the boro glass here is branded Schott/Duran so...) that I use for adding water after the first base and siphon. Love the way these bottles from 100ml to 10 000ml all have the same sized lid.

So to make sure: you think separating the harmine/dhh (ammonia/VDS) is just as clean and pure as after a manske? My ultimate goal in this would be creating some more THH, my new favourite harmala.