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A 72 hours Syrian run

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pastanostra

pastanostra

Rising Star
Hi Nexians,

It's with much entousiasm that this week we ran a 72hours extracting rue.
This extraction told us a lot and rewarded our mind. This extraction is fantastic, playing with ph and learn how to be efficient in filtering was much more than we think, it's a real connection.

Our main objectives were :

- First extracting rue
- Doing manske
- Basing with sodum carbonate
- Seeing harmine and harmline precipitation
- Have possiblity to try an MAOI (never tried)
- Learning from tao of Rue
- Take pleasure

The yield was not a objective but much more understanding the method of extraction with very good tek (manske, small basing). We were not so confident with our PH meter (result / using) and rue told us to observe, to not trust allways machines and apply affirmation and action based only on.

This will be a bit condensed text, all was recorded on our lab book. I had a bluescreen while typing the text :(

We started with 100g of Rue seeds.
Not grounded, seeds were boiled with 2L water & 5g acid citric (PH = 2,31) during an hour.
Until reduced, tea has been blended (softer than dry) then 2L more water only added.
At 700mL, tea was pourred out into metal strainer, then 2l acidic water added to the seed, boiled like before.
3 boils has been done.
We wanted to work a lot, and have the necessary time for it, so we started a 12h filtering run.
While it passed trough a filter at a speed of 1 drop for 5s (at the ended) it seemed good for us.
We reduced the tea to 500mL and filter once more.
We prepared a solution of 20g lye for 200mL water and added 70mL of this solution

The PH of acidic solution before basing is PH = 3,45
after basing we went to PH = 11,45

Precipitate Crashing out

1523832875.jpg


This has been decanted few hours, to do a maximum, the basic solution has been keeped for additionnal results.
Freebased harmalas has been dissolved in 200mL vinegar + 100mL water, then filtered.
The PH is 3,75 before manske and volume is 350mL.
Warmed acidic solution then dissolved 36g of rock salt, after salting PH = 3,5
We putted this to the fridge for the night.
Aggregate precipitated then filtered.
Dissolved precipitate in 250mL hot water PH = 3,8
A second manske is done with 22g of salt then put in the fridge, after few hours we observed theses tiny needles

1523833471.jpg


At this point we were very confident for the experiment (regardless to the yield).

Alkaloids were filtered then dissolved in 80ml water.
A sodium carbonate solution has been prepared, not fully saturated (PH = 11,1).

We started adding carrefully small drops of base in the harmalas solution

1523833716.jpg


And after stirring gently started to see harmine precipitation

1523833818.jpg


After a bit of settling, we see harmine here, at this point PH = 7,30 , 8mL of sodium carbonate solution were used.

1523834117.jpg


Our choice was to not interrupt basing for harmine separation but to continue the process.
We continued to add more base until we reach PH = 9,5 then raised to 10,5 , the color became fluorescent yellow, under normal light o_o

1523834293.jpg


1523834388.jpg


What do you think about this yellow ? Did you encountered something like this ?

Then wee let settled few times, and started water wash until solution become clear and ph downed.
Our distilled water wich was used for the wash have a PH = 8,6 , our tap water have a PH = 8,4, do you find theses values normal ?
At our 7th water wash PH = 9,1 , between 4th and 7th wash we passed from 10,1 to 9,1
Too hard to get lower values.
After 2L of washing distilled water, we decided to let the harmalas drying.
After many hours of drying we got 1,8g of this product :

1523835046.jpg


Do you guys, with you eyes and your experience in harmalas the product seems good ?
Should we acidify one more time then rewash it ?

Many thank to the Nexus for having shared theses great informations

Cheers Nexians
 
nice work :thumb_up:
your initial tea preparation seems good so you have lost yield in other steps.. i would say most probably in the manske.. i usually use twice that amount of salt/volume.. but anyway the product looks good :)
i have noticed the yellow color in basing step when using sodium carbonate.. and then adding few drops of NaOH solution will resolve that color although i didn't notice any significant precipitation.. i usually base my harmalas drop by drop with NaOH until the yellow tinge goes away. then i do few water washes and i make sure to remove as much as i can of the water before drying.
and yeah distilled water should have ph 7 and drinking water should be around that too so maybe your ph meter is not working well.
Here in the pic you can see what i mean by yellow tinge.. the 2 shots are just 1 drop of strong NaOH solution away
 

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You did very well!

One trick you can do is to leave the reduced tea sit overnight. The finest insolubles will settle and it will be easier the decant/filter the supernatant liquid. The bottom gunky part is hardest to filter but something like cheesecloth will do (I use cheeseclots and then cotton plugs + vacuum).

Another trick is to re-acidify (salt) your alkaloids in a small amount of water, filter, re-base, filter, and THEN do Manske. You will be surprised how much gunk gets removed by just switching to acid one more time. The Manske step will then work with less impurities thus giving bigger crystals and higher yield.

Washing the freebase alks with clean water few times also helps to improve purity.

Finally, if you have access to vacuum filtration setup with Buchner funnel, you can pass the acidified extract through a bed of Celite (or food grade diatomaceous earth). This will remove the finest impurities. I sometimes get tea that is so clear it even does not start to crystallize until scraping the beaker. It looks like red wine :)

Of course doing the Manske more times will push the purity further since this is basically recrystallization by dialysis.
 
The yellow color is due to very small amounts of harmaline still remaining dissolved at pH 10.5. If filtered and then based with copious NaOH, the solution will turn clear and a tiny fluffy layer of harmaline precipitate will form.

The pH of your tap water means that you have "hard" water. Small amounts of calcium carbonate could get trapped in the freebase while washing. These are harmless and there would only be minute quantities present. You can wash with store bought demineralized water instead if you want to prevent this.
 
pitubo said:
The yellow color is due to very small amounts of harmaline still remaining dissolved at pH 10.5. If filtered and then based with copious NaOH, the solution will turn clear and a tiny fluffy layer of harmaline precipitate will form.
Click to expand...

Hah! Maybe that's the reason why I never get harmaline. It seems requiring way higher pH than 10.0 to precipitate.
 
blue.magic said:
Hah! Maybe that's the reason why I never get harmaline. It seems requiring way higher pH than 10.0 to precipitate.
Click to expand...
?!?

Not at all, in my experience. In fact both harmine and harmaline appear to be precipitate much earlier than the long cherished values based on their calculated pKa's.

Did you attempt to perform any rigorous testing of your results and procedures using eg. tlc?
 
Hello Guys,

it's a pleasure to ear your comments, thank you very much.

We know more or less where we lost goodies, and the 2nd manske (not enough room for liquids) was it,well our filtering tek too, loss some mL each filter (above 25filter & 30 cotton ball used)
We have a buchner funnel but we clogged it in our final filtering stage, it have a ceramic or cellite filter, but very small (15/40 microns). Actually acetic acid is on to dissolve. It work nearly normally with acetic but when it's water, filtering is harder. I choosed this cheap one for the pump ^^, Does a Lye solution can help cleaning ?
Our paper filter are chinese and we can't read the size of holes.
As said, Tao of Rue really teached us, and we learned a lot.

In terms of taste, i tasted a bit of extract on my tongue (maybe 1 or 2 mg) and i noticed no taste or a very little bit of "i don't know what" and a bit os basic feelings (like sodium bicarbonate ), but this test has been done at woke up before cofee ^^. During cooking, the smell of rue isn't bad and unpleasant, we found this plant really cool to work with, according to the tao of rue or in incence. The standard use of no or very little harmfull chemicals is very great (for our earth and us). We have passiflora as local source of MAOI, and actually didn't find one more documented / tested
With your messages and observation we're really confident on the final product and will test it on it's own, there after with another extract. We're confident too for the MAOI diet, as from this new year, junk food is reduced to it's minimum, alcool is consumed maybe one or twice a month in small quantities, no medication, and we used to feast above once a week. This permitted to us to live very different kind of psychedelics experience (compared 10 years ago), no eat during one day or two can be handled without noticeable impact on being tired and social life (just a big hungry after :lol: ). We heard too that harmalas seems to be safer than other MAOI in terms of diet.
We'll plan to make a changa with 300mg harmalas, 1g acacia simplex extract,450mg damiana, 450mg passiflora edulis dried leaves, 100mg peppermint,

Our solution before 2nd manske was pretty clean looking too :

S97dVPL.jpg


As we collected all the rinse solution we could later continue our test & saw additionnal yield.
After the 1st manske, le resulting filtered solution has been reduced, added a bit of salt, and go to the fridge, but didn't saw any precipitate.
For the 2nd manske it hasn't been done due to no more space / equipment lab (that's an error), here the 2nd manske with no room :

AMfuomr.jpg


I like this basic splash onto harmine precip.

aojzNam.jpg


We'll not plan to do lab analysis on this extract, as it's a pretty common plant, and i trust in your visual analysis. This extract could be named "Red Harmalas" ?

Last pic with comparison with end solution (on the left at 5th water wash) and the washed extract of the first basing step (on the right 5th water wash)

EZ7E2vn.jpg


Cheers all
 
pitubo said:
blue.magic said:
Hah! Maybe that's the reason why I never get harmaline. It seems requiring way higher pH than 10.0 to precipitate.
Click to expand...
?!?

Not at all, in my experience. In fact both harmine and harmaline appear to be precipitate much earlier than the long cherished values based on their calculated pKa's.

Did you attempt to perform any rigorous testing of your results and procedures using eg. tlc?
Click to expand...

Not TLC, but the pH separation never worked for me even with careful titration and calibrated pH meter. Either my rue contains no harmaline at all, or I am doing some mistake in the extraction. At pH 8-9, everything crashes out and then nothing more. I will try decanting the yellow liquid and adding excess NaOH to see if anything will precipitate...
 
blue.magic said:
At pH 8-9, everything crashes out and then nothing more. I will try decanting the yellow liquid and adding excess NaOH to see if anything will precipitate...
Click to expand...
That is precisely my point: at pH 8-9, both harmine and harmaline will have mostly precipitated already, with perhaps only small amounts of harmaline still remaining in solution (the source of the yellow color).

When I dissolved harmala HCl crystals from a purified rue extraction, the pH read well below 7. Upon careful basification, harmine started dropping out at pH below 7 and most harmaline below pH 8. This confirmed to me what was earlier documented in the VDS thread, and contradicts some long held beliefs documented here in many places.
 
^^^ to complete the above, the pH points are sensitive to circumstances like concentration, salt contamination and base used. The VDS mechanics won't always apply imho. For example I can't get it to work with lye.
 
Thanks Jees and pitubo. Now this is confirmed, an older document from Phlux also confirms this as he merely neutralized the solution and already got "almost pure harmine", filtered and only then proceeded with further separation.

I will try it again with ultra pure free base harmalas, dissolve in dilute HCl and titrate with dillute ammonia and see.

Keeping the solution at low concentration (excess volume) might help too.

Sorry, OP for stealing the thread for this discussion.
 
VDS kept around 15 and 20 mg of mixed harmalas per ml of total liquid (water + acid), then he start to base.
If you rise concentration the freebase precips get more sticky on the vessel walls, pH probe etc (especially using carbonates to base then it can get messy).
If you lower concentration then the pH depressions get fainter and flatter, the separation becomes thus more difficult to pin point.

One does not have to follow VDS mechanics by any means, things will precipitate under any base and a wide range of concentrations eventually. Though it will happen without pH depressions as handy indicators.
 
Jees said:
VDS kept around 15 and 20 mg of mixed harmalas per ml of total liquid (water + acid), then he start to base.
If you rise concentration the freebase precips get more sticky on the vessel walls, pH probe etc (especially using carbonates to base then it can get messy).
If you lower concentration then the pH depressions get fainter and flatter, the separation becomes thus more difficult to pin point.

One does not have to follow VDS mechanics by any means, things will precipitate under any base and a wide range of concentrations eventually. Though it will happen without pH depressions as handy indicators.
Click to expand...

I tried basing with ammonia today but still no luck. Everything crashes immediately and no separation occurs.

Here is my post with photos of the experiment.

I have used 5 grams per 300 ml water, that is 16.6 mg harmalas per ml. I have not observed any sticking to probe, walls or the stirrer.

Everything was perfectly clear and smooth, just not separating at all.

The harmala freebase was made by myself according to the teks in wiki and I always add excess base (over pH 11.0) to make sure I get most alkaloids. So either there was no harmaline in the rue or something weird happens.

Is there any simple test for a presence of harmaline? I don't have access to TLC right now, nor have time to learn it.

Here are the resulting fractions from the pH separation:

PzTcVYB.jpg
 
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