The last weeks I was busy with harmalas.
I just want to sum up some stuff I figured out and some results of extraction.
Mostly for my self, but maybe s.o. find it usefull.

So the two main alkaloids are Harmine and Harmaline (also know as DHH). So called Harmala-Alkaloids or Harmala-HCl are a naturally mix of Harmine, DHH and small amounts of other alkaloids.

Both Harmine and DHH do fluorescence up VERY bright in green-yellow under UV-B if in acidic solution (less to no fluorescence at higher Ph).

Harmine is a reversible MAO-A inhibitor (RIMA).
DHH is also a reversible MAO-A (and maybe MAO-B) inhibitor and twice that potent (= half dose of Harmine).

Harmine freebase has (very small) needle-style crystals.
DHH freebase has (very small) plate-style or leaf-style (sometimes up to a few mm) crystals.

Harmine HCl has fiber-style crystals.
DHH HCl has has unknown-style crystals.

All (FB and HCl) can be dark brown to red to (almost) white (when thoroughly cleaned).

Both freebase alkaloids have almost no taste.
Both HCl salts have a very bitter and unpleasant taste.

With mecke or mandelin reagent test it is easy to distinguish them.

DHH can be transformed to THH, with is no MAOI, but a weak SSRI (serotonin re-uptake inhibitor). This reduction can be done from mixed harmalas. Separation is easier after the reduction.

You can smoalk freebase or HCl, they seem to need quite high temperatures for evaporation but are not heat-sensitive (will not burn/decompose so easily).

for changa or Harmala-enhanced leafes it+s easy to dissolve the HCl in water and then apply on the leaves.

freebase is difficult to dissolve in most common solvents (beside acidic water, but then you'll have salt once it is dry again).

for oral consumtion i prefere freebase as it has almost no taste. what is not taken up by your mucous membrane in your mouth will be dissolved in your stomach by your stomach acid and then absorbed.





About extraction:

its easy, but it will take some time for depositting, decanting, filtering, warming, cooling, drying.... Days. or Weeks.
It's good if it can stay somewhere and you can work there every day for 5-30 minutes.


With a few boils in plain water (or maybe even better water with acedic acid @ ph ~5) you can extract the alkaloids easily.

When you keep the seeds in a closed cloth bag during boiling you can just hang them up to drip over night before the next boil. That saves you a lot of filtering hassle.

Grinding the seeds will increase the yield, but also the filter job.

Make rather more boils with just enough water to cover the seedbag than less boils with more water.

Collect all the tea in one or more containers and let it settle for a day or two. then decant. Now you can filter, but that might not be necessary jet. It might be easier to wait with the filtering until you solidified and resolved the alkaloids (as freebase or HCl).

then its time for the next step:

To clean up further, you can either do one or more "manske" or base-acid rounds or a mix of them. With both methods you will loose a few % of the alkaloids in every round, no big difference in loss between them.

Base-Acid rounds are faster (no heating and cooling necessary) but you'll need lye or ammonia, both corrosive chemicals you might not get so easy and cheap. Sodium might work too but bubbling CO2 caused some trouble to some people. For the last basifining its best to use foodgrade ammonia, as any contamination in the end product will evaporate together with the water. If you don't have ammonia use foodgrade soda or foodgrade lye.

For Manske you'll need just salt (NaCl) water, heat and time.



Base-Acid:
>>>>> don't use soda if your solution contains lot of acid, it might end in a mess <<<<<
while gently stiring, raise the Ph of your acidic acid / harmala solution slowly with lye or ammonia to Ph 10, then filter or wait for the percipate to settle, then decant.
Dissolve the freebase ( filter cake or the sludge left from decanting) in 5% acidic acid, filter out any impuritys, raise the Ph again and collect the freebase. after some more rounds like that the filter cake (=freebase) should get brighter and brighter, almost white when dry.
You can additionally wash the freebase after each round with water (raise the Ph if necessary to 10 with lye, ammonia, soda or ...)


Manske.
If you have a tea with medium or low alkaloid concentration, heat to near boiling and add the same amount of hot saturated NaCl salt water. Cool slooowly.

If you have freebase or salt harmalas: Take note of the aprox amount of dry alkaloids. Dissolve the freebase in as little clear vinegar or acedic acid as possible, then fill up with water until you have ~50ml for every g freebase.
If you have HCl just dissolve them in 50ml water / g alkaloids.
heat up to almost boiling and add 4,2 - 5g NaCl for every g freebase. Cover the vessel / pot and wrap with blankets to sloooow down the cooling process. Once at room temp, you can move it to a fridge for further cooling.
Then filter out the fiber-like Mix-Harmala-HCl crystals. You can now dry them and enjoy or repeat manske for cleaner product. just dissolve the Harmala-HCl in 50ml water / g alkaloid, heat, add salt, cool slooowly, filter, repeat...


If you want to isolate Harmine and DHH or THH:
If you have Harmala-HCl salt, dissolve it in ~10ml water / 1 g Harmala-HCl.
If you have Harmala-freebase dissolve in as little acedic acid / vinegar as possible, then add water to total ~10ml / g freebase.
Now slowly add ammonia. If working with small amounts, use diluted ammonia drop wise, if working with bigger amounts, for example 60 g freebase use 1 or 2 ml 9% ammonia at once. gently stir and observe the Ph-level (a cheap digital PH-Meter for a few € from ebay will work great).
You will notice a depression or even a drop of Ph at certain points. That will tell you when to stop and decant / filter before continuing.
For example: Ph stedily rises up to 7,5 and then stops or start to drop. FILTER. continue with ammonia until you pass that mark again ( for example 7,4 ... 7,3 .... 7,2 ... 7,3... 7,4 ... 7,5 ... 7,6). FILTER . Continue like that until Ph 10.
That way you will get two big and some small fractions. The first of the big fraction is the Harmine, and the second big fraction is mostly DHH (and some Harmine). The other small fractions are mixed stuff and may contain even other alkaloids.
You can repead this separation on the harmin and DHH fraktions for further purification.
You can also repeat the process on the combined small fractions or just keep the small fractions all together and throw them in before the separation of your next batch.



If you need to clean tools or vessels etc with alkaloid-remains first wipe them with a small piece of filter paper or paper-towel and collect them together with all used filters and once finished you can extract any entrapped alkaloids from it. The extract of them can be purified as described below or stored and processed with your next batch.

•DHH can be transformed to THH, with is no MAOI, but a weak SSRI (serotonin re-uptake inhibitor).
-Take the 'weak SSRI' thing with a grain of salt, thats based on experiments with slivers of rat brains. I've found THH to be a mild antidepressant in one small dose and a mood enhancer in one moderate dose, no need to take it for months and get addicted like prescription SSRIs.

•With a few boils in plain water (or maybe even better water with acedic acid @ ph ~5) you can extract the alkaloids easily.
-I tested this, extractions with acetic acid to pH 5 versus no acid which was naturally pH 5,9 gave identical yields.

•When you keep the (whole or better grinded) seeds in a closed cloth bag during boiling
-Grinding seeds will just test the limits of your sanity when you try to filter. So at least 3 long simmers, 4 is better, I do 5 on large batches to get an extra 3 doses out of 250g of seed.

•Base-Acid rounds are faster (no heating and cooling necessary) but you'll need lye or ammonia, both corrosive chemicals you might not get so easy and cheap.
>>>>> don't use soda, it might end in a mess <<<<<
-Sodium carbonate works just fine and is very safe. Its available as washing soda or you can bake baking soda in the oven to make it. If there is lots of acid involved it will foam up.

•while gently stiring raise the Ph of your acidic acid / harmala solution slowly with lye or ammonia to Ph 10
-This is quite in accord with what I have found, after basing to pH 9,8 and clearing the solution with a centrifuge even ammonia failed to precipitate any more alkaloid from the remaining solution.

•Manske.
Take note of the aprox amount of dry freebase. Dissolve the freebase in as little clear vinegar or acedic acid as possible, then fill up with water until you have 50ml for every g freebase. heat up to almost boiling and add 4,2 - 5g NaCl for every g freebase.
-This sounds like a clumsy way that will be prone to error. You can use 10-15g of rock salt dissolved into each 100ml of seed tea or, if working with more concentrated or purer solutions, you can mix the hot solution with 1/2 its volume in saturated salt water.
What matters is the concentration of salt in the solution about to make crystals, not grams of salt per gram of freebase.

Overall it sounds like you have a pretty good grasp of things

Oh, one tip, if you plan to make THH from the DHH just do the acid-metal reduction on the harmine-DHH mix and then separate them. It makes them easier to separate as there is no delicate depression dance, they simply precipitate at different pH's. You get nice yellowish white harmine as a bonus.

Thanks for the input Elrik!

I'll clarify, update and extend the post over the time, so that's only a first script...

About grinding the seeds:
If you keep them in a bag all the time, its not so hard to handle. Waiting and decanting helps too.

So this depends on the availability and price of seeds.

About manske, I found out, that the best salt concentration also dependents on the concentration of alkaloids.
> with higher alkaloid concentration you can work with lower salt concentrations.
> The loss of alkaloids depend mostly on the ratio alkaloids:water.
> too little water, and the crystals have no space to form.
> too much water, and you'll loose more alkaloids than necessary (and waste more salt).
> lower salt concentration in the water means also lower salt contamination in the end product.
So the ratio alkaloids:water:salt is important.
I did recover ~98% (calculated as freebase) with 1:50:4,2
I verified the results by baseifining the saltwater and almost nothing precipitated.

I also tried Phlux way and added hot saturated salt water 1:1 to quite concentrated hot freebase-acedic-acid-water solution. I instantly got a lot of precipitate that filled all liquid, no space or time left for nice crystals.
Thats why i added the alkaoids to the ratio.

Good summarization Elrik. Now my turn:

Donts:

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* Dont grind.
* Dont boil. (Acidic fractions, Only simmer)
* Dont go below 5.5 ph
* Dont reduce
* Dont chase after yield, chase after purity.

Dos:

---

* Dedust (shake dry seeds in the strainer)
* Defat with acetone in the fridge for 24 hours
* Boil first fraction in high PH water and discard it, subsequently washing the seeds under tap water
* Use H3PO4 instead of vinegar
* Basify, settle, decant and then filter
* Pre-manske boil with some activated charcoal
* Successive double manske for cleaner yield

I don't grind the seeds, and waiting/Decanting in the fridge works so well that I don't filter the initial water extract. Not sure if that plus still applies to ground seeds (?).



Was that done with cleaned harmalas? Harmalas that still have other stuff in them can behave differently (e.g. have increased solubility in water).

The starting harmala acetate concentration is important, that's a good point. In a simplified ideal system I think the equilibrium equations say that for a given harmalas concentration (call it [HH+]) there is a critical NaCl concentration (call it [Cl-]c) at which precipitation starts and is inversely proportional:

[Cl-]c =K/[HH+]

Where K is a constant (for simplicity we will consider one harmala alkaloid in solution). So very simply, double your harmala acetate concentration and the HCl salt will start to crash at half NaCl the salt concentration. Quadruple the starting harmalas and precipitation starts at one quarter the salt concentration, etc.

The effect on this starting point on the harmala recovery ratio (R) as more salt is added is interesting. Let's call the added [Cl-] salt to harmala molar ratio x, also let's call the critical [Cl-]c molar concentration relative to harmalas y. Then, I think,

R = 1/2 * {x+1 - (x-1)√(1+4y/(x-1)^2)}

This describes how nothing precipitates until x = y (at which point R=0, before that, the recovery rate is negative which just means nothing has crashed yet). At higher x, R tends to 1 (=100% recovery) with an assintote behavior approximated by,

R -> 1 - y/(x-1), for x >> 1

Where we can see the advantage of setting the solution to a low y (that is, have a higher harmala concentration so the critical salt point is lower).

Of course in practice harmalas can't be too concentrated as we want some room for xtals and other stuff to separate, so there is a sweet spot.

With the equation above one could get an idea of the recovery rate as salt is added based knowing the starting harmala concentration and noting when precipitation starts.

Below are plots that illustrate this, notice how for dilute harmala solutions (y ~ 10) the tapering to get close to R = 1 (light yellow region) is not very good, while more concentrated solutions react quicker and better to salt (y ~ 3). Also, since NaCl salt concentration can't go up beyond it's own solubility, x has a cut-off, and significant losses could happen if the initial harmala concentration is too low (if the tapering region cannot be reached).

Disclaimer: This has not been double checked and could be wrong. These are just estimates based on the most basic equilibrium equation which is a first order approximation only. Also, on practice something other than harmalas (e.g. large proteins) may precipitate first at a low salt concentration which may be receiving if trying to figure out y.

I like this thread, will add my observations:

Long boils are not needed, you can extract most of the alks by really quick pulls. Last time I did 5 boils, each one for 5 min and yield was the same as with longer boils.

No fine filtering of initial water pulls is necessary, even with grinded seeds. Just filter it through some cloth.
Letting to settle is also not really necessary, you can base initial tea directly without it.
You are going to fine filter and purify it in next steps anyway.

pH for precipitation of harmalas is definitely lower than pH needed in case of dmt or mescaline extraction. So far, I thought it is pH11 but seems that it is even lower. I use KOH as a base and it works perfectly.

This I will have to test! Lately I've been getting each pull to a mild boil for a minute, then easing off to a very light simmer for an hour before turning it off and letting stand covered for 3+ hours to cool off enough to not be scalding. That always leaves me allowing one pull to 'cool' overnight.
This should be left as a judgement for each person. It's my opinion that people are being strongly encouraged to chase higher purity than most people really need. Just basing the tea, letting settle, and doing one manske on the sludge at the bottom will give people a usable and very much concentrated product.
I like to purify further because for me its fun and going farther with acid-metal reduction seems creepy to do with an impure product.
This has been on my list of things to try! I've noted that 250g of seed can absorb 1L of near boiling water with almost nothing left so I thought to make them absorb a sodium carbonate solution, leech that out with water, then do a vinegar-water extraction series. I don't imagine it gets the red out, for you does it reduce the viscous pectin-saponin like sludge that gets in the way so much?

I would say that such long boils and maceration in hot water will extract more of the other stuff from the seeds. Alkaloids are extracted quickly.

It does both reduce the red and the sludge

nice

Wow, so much high quality input, thanks!

About boiling process: I always heated the pot with the grinded seeds and water to boiling or near boiling, then moved it from the stove to a place where i can hung the bag with seeds above the pot and let it drip overnight.
So no long boiling or soaking.
The next morning i decanted the liquid from the pot to another container and started a new boil with the seeds.
One or two days later i did one more decanting and the liquid was already going quite well thru a coffee filter.
If your in a hurry that's not the best way, but time and decanting really did the job for me.

I'm now experimenting with an old juice centrifuge, equipped with coffee filters, to easily filter a few litres of neural or weak acid brew. Might be handy also for other projects....

I didn't encounter any problems with fats or oils, so i don't see a reason for the acetone defatting. Maybe this depends on the strain of rue?

Reducing the amount of red with a basic water pull could indicate you are removing harmalol (which the usual extractions do already).