Optimizing First Manske

[blue.magic]

I am trying to find good parameters for initial Manske precipitation, but it never seems to work right.

I wash the free base alkaloids several times, re-acidify (with acetic acid), re-filter, re-basify and wash again several times.

I then try to find good parameters for Manske, e.g.

- harmala concentration: 1.5% (15 g/L)
- acetic acid concentration: 7% (70 g/L)
- salt concentration: 10% (100 g/L)

Once the solution is made, I heat it above 70 °C and let cool down slowly.

Unfortunately, I usually get only small amount of dark brown/red crystals and most stay in the solution.

The problem is of course there are still too many impurities and it is hard to guess the good concentration for harmalas.

I am also thinking about using HCl instead of acetic acid, since the hydrochlorides are less soluble in water, thus might crystallize more easily.

 

[Jagube]

I'm not sure it has to do with impurities; I only basify once, wash, acidify and Manske that directly and it works. My harmala yields are in the area of 5% (however impure they might be after a single Manske cycle).
But I boil the seeds whole, not ground, so my soup may not contain that many impurities to start with?

I am also thinking about using HCl instead of acetic acid, since the hydrochlorides are less soluble in water, thus might crystallize more easily.

Even when you use vinegar to dissolve your freebase, it's only the hydrochlorides (which Manske produces by Cl ions from the NaCl displacing the acetate ion) that crystallize.
If you dissolve your freebase with a hot HCl solution, then after cooling down, some other alkaloids, whose HCl salts are poorly soluble in cold water, may precipitate. The main point of Manske is to separate harmine and harmaline from those other alkaloids.

 

[blue.magic]

If you dissolve your freebase with a hot HCl solution, then after cooling down, some other alkaloids, whose HCl salts are poorly soluble in cold water, may precipitate. The main point of Manske is to separate harmine and harmaline from those other alkaloids.

Good point.

I read that the toxic alkaloids vasicine and vasicinon are poorly soluble in water (unlike beta carbolines) and most of them are removed by making tea and filtering it.

As for other alkaloids, my thought was that since harmine/harmaline are major ones, the mere crystallization will resolve them from others.

The first Manske never works for me - even though I filter the tea like crazy, even with vacuum, many times. The first Manske is always just a tiny amount of dark crystals in a liquid that is still full of harmalas.

The second Manske is quick and easy with high yield, but I lose almost half of the product (if not more) in the first one. Hence I am looking for some guidances...

How much water do you use for say 100 g rue seeds? How much vinegar and what concentration? How much salt?

 

[padawan]

My first manske's are always weird but I tend to get the longest, thickest and darkest needles - a couple of days ago a first manske produced 5cm long needles, about 1mm in diameter. I basified the solution after filtering the needles off and ended up with about the same weight of harmine/harmaline HCL as "other" freebase alkaloids.

Generally, I use the phlux method: acidify with just enough 5% acetic to dissolve the FB for the first manske - for subsequent manske's it's hot water only. Separately make a salt saturated solution (as much as will dissolve) and add an equal volume to my dissolved HCL harmalas. Overnight cooling to room temp then into the refridgerator in the morning for a couple of hours.

This extraction I'm freebasing out all the leftover alks after each manske. I'll combine them and see if I can squeeze any more harmine/harmaline from them. Will be very interesting. I'm also tempted to try a PH separation on the unwanted alks to see what happens.

 

[Jees]

...- salt concentration: 10% (100 g/L)...

10% salt has not worked for me, double it? 20 Has been my usual go to.
In padawan's recipe above it's around 17 to 18%, that's more like it.
VDS goes for 23.5%:

2.2 Separation of harmine and DHH from the other alkaloids
The total mass of alkaloids was dissolved in 125ml of hot vinegar 7% and this solution was left to stand for 6 hours to let the fine plant material settle. Then the supernatant was filtered through fine filter paper and reheated. In another recipient, 88g of NaCl was dissolved in 250ml of boiling water and this solution was added to the hot extract. The mixture was then allowed to cool slowly for 12 hours...

One of the factors in play is not only salt concentration but alkaloid concentration as well. This last is usually overlooked.

Btw I've used phosphoric acid before with very good results for manske, just telling.

...I basified the solution after filtering the needles off and ended up with about the same weight of harmine/harmaline HCL as "other" freebase alkaloids...

I always end with a fluffy slime unable to filter or catch
I also noticed that the nicest of needles do not come from the very first manske.

 

[Jagube]

I read that the toxic alkaloids vasicine and vasicinon are poorly soluble in water (unlike beta carbolines) and most of them are removed by making tea and filtering it.

As for other alkaloids, my thought was that since harmine/harmaline are major ones, the mere crystallization will resolve them from others.

What about harmol and harmalol? IIRC they're more prevalent than the vasi* ones, and in the same order of magnitude as the major two.

I don't know much about them and they may be beneficial, but when my intention is to obtain reasonably pure harmine and harmaline (for THH synthesis) to make a Caapi copy, I want to make sure my Manske removes all other alkaloids.

Btw I've used phosphoric acid before with very good results for manske, just telling.

I'm wondering what your criteria for "good results" were? Mine would be to obtain a reasonably pure harmine and harmaline mix, and I wouldn't know how to verify that that was achieved (i.e. no other alks or other active compounds; I don't mind inactive impurities so much).

But using HCl in the *first* Manske, assuming more Manske cycles will follow, could work as a step to remove inactive impurities. It would be a bit like an acidification / basing cycle, but maybe a different fraction of impurities would be removed (i.e. soluble in acidic solutions - which neither Acid nor Base filtering removes).

 

[blue.magic]

But using HCl in the *first* Manske, assuming more Manske cycles will follow, could work as a step to remove inactive impurities.

Exactly, I need to strip off as much impurities as possible before acetic acid / NaCl precipitation.

I was even thinking about not using any salt, just water to precipitate some hydrochlorides, then reducing the water and maybe adding some salt.

The initial runs should remove most of the impurities, making the real Manske step more quantitative and better controlled.

Another reason for avoiding lots and lots of salt is to reduce water pollution and to make the process more efficient.

So far I try 20 g/L of impure alkaloids and 10% salt, but it seems the salt concentration is too low and alk. concentration maybe too high. Next time I will go for 10 g/L alks. and 20% salt.

In my experience, using 15% salt or more crashes everything too quickly. The 3rd and 4th Manske works perfectly with just 7-8% salt.

 

[Jees]

...In my experience, using 15% salt or more crashes everything too quickly. The 3rd and 4th Manske works perfectly with just 7-8% salt.

I stand by this

...One of the factors in play is not only salt concentration but alkaloid concentration as well. This last is usually overlooked...

The salt numbers get affected seriously ime.

 

[exquisitus]

10% salt has not worked for me, double it? 20 Has been my usual go to.
In padawan's recipe above it's around 17 to 18%, that's more like it.

similar experience here.

 

[blue.magic]

Yes I did a little experimentation and 20% salt works on crude, but crashes too fine harmalas - but 15% might also do the trick. Since 26% is maximum possible concentration, 17-18% seems sensible tradeoff as suggested (thanks). I would keep the crude harmala concentration below 15 g/L as otherwise there is too much impurity.

I also found adding salt immediately crashes out lots of impurities (even if the solution is clear and passes filter easily before salting). I am not sure how much harmalas are trapped in tha impurities, but it may be a good idea to filter the hot Manske solution before leaving it to crystallize.

Images will follow :thumb_up:

 

[Asher7]

@ Optimize, if you follow the steps in The Tao of Rue Extraction on the WIKI it will work perfect. I do about 1/2 pound and boil it down to about 2 cups and base it. Take the base and dissolve it in 1/4 cup vinegar and 1 1/4cup water, get it just shy of boiling and stir in 36-37 grams of salt. Fully dissolve and pour into your crystal growing cup. You should have a boatload of crystals in about 3 hours.

Also I saw it mentioned someone doesnt grind their seeds. So far I seem to be getting about the same results whole/crushed but crushed puts 10 times the sludge as boiling whole. Boiling crushed adds about 10-15 more filter steps to get the light tan/white you’re aiming for.

Edit: I was going to post a pic but it says jpeg aren’t allowed even though listed. I’m probably doing something wrong.

 

[blue.magic]

Thanks but this is not my experience. I followed both popular teks from Wiki, and the crystallization does not work every time like in the Tek.

This is because there are other factors in the game which I am try to manage.

There have also been made many improvements from Nexians which I like to incorporate.

Another reason is that I am working with large batches and really want to reduce amount of salt needed. Large scale production should not be discussed here so I won't expand on that...

Yes crushing the seeds is unnecessary - it adds very little alkaloids and whole lot of sludge. The alkaloids and concentrated in the seed shells anyway.

I will add photos from my last run (imgur is good for posting pics as it supports bbcode forum links) when I get to it. I had some interesting findings.

 

[Asher7]

Oh so you’re trying to tweak the recipe a little? Why is it you’re trying to avoid salt?

Also what are some of the improvements nexians have added to the process?

 

[Loveall]

Hello.

Some simply do a short pressure cook (~20 min for example) with water and whole seeds (no vinegar). The resulting extract is allowed to settle in the fridge overnight and decanted to give a clean liquid (you can filter too but decanting alone is pretty good if allowed to settle well). Then base and recover the solids* with more settling/decanting. That's clean enough for some after you rinse out/evap the base.

As far as manske, this is how I like to do it: once acidified simply add salt to get to ~20% NaCl or more. Fine crystals/powder should crash out quickly. Put the jar in a pot with water on the stove top and let the water in the pot get to a boil. Eventually the fine powder in the jar will redisolve thanks to the heat. Then turn off the heat and leave everything alone (e.g., overnight). After a few hours it will be at room temp, then move it to the fridge. The next day there will typically be long needledls thanks to the slow temperature drop and crystalization. Remember Jees mentioned the temperature profile in another post? A slow cool down from a saturated solution seems to work well.

Patience/lazyness is good. Just allow time for settling/cooling/crystalizing. Not a lot of active work, just takes a few days. In my experience this is easier than forcing the issue with quick filtering and hasty crystalizations. Rue seems to enjoy a chill Zen approach However, this is just my preference and each person may enjoy a different approach.

*The first base step may have some harmalol in the alkali liquid. It's possible to recover it but a bit tricky. It can give a red color, and washing the decanted freebase alkaloids with fresh alkali water before going to the next step can remove the harmalol effectively if that's what you want.