Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols

[endlessness]

Makes sense

Weird things happen in chemistry in these complex solutions, hard to say what happened there exactly

Awesome experiments either way!

 

[Jees]

... I used the other half of post #134's reduced and charcoal-cleaned solution (pic01). To this I added sodium BIcarbonate until 10% remained undissolved at the bottom underneath the zinc salts (pic02)...

* * *

Endlessness it would be great to have stuff tested more analytical :thumb_up:
If some one in the south of Holland can perhaps?

* * *

An1cca, that 10% rule is no good when alks are in as I mentioned in #131. It barely approached 7 and therefore I did more to 20% layer undissolved sodBIcarb to get to 7.5
The tests in water without alks cannot simply be extrapolated to alks. So if you did 10% and I did a 20% up to 7.5 , we might see a difference.

I see yes a slight mist in the 7.5 by now *SEE PICTURE* (was pH 7.5 with sediment, 8 without = meaning filtered). Since it is something that takes time to form it's not alks (I suppose) but straight ZnCO3 peeping trough. The sodbicarb seems to have more trouble taking down ZnCO3 when it's a mix with alks. In plain water things were more favorable.
Since you got "only" 10% you're pH was (as I've seen on my side) below 7, and a lot of the ZnCO3 was not precipitated, which you encountered later.
I, on the other hand, went to 20% and got to pH 7.5 / 8 and therefore got much more ZnCO3 down and my solution stays more clear?

Note:
Thinking like: well if all it takes is more sodBIcarb then just lets do that: to this there are limits, because that layer of undissolved must be washed to recover your mother liquid that fills it. I'd say 20% is max to make it workable, but just sufficient for getting pH 7.5 in my case that is.

So I think you had a ton ZnCO3 remaining after the 10% sodbicarb wash + post wash.

I never dump sodcarb powder, I always make a saturated solution. For sodcarb that is even a warm solution I titrate with. I can imagine in a (loids) mix the sodcarb has a harder time to go into solution, I think this is a great opportunity lesson for us all to better add a solution of powder, not powder.
For sodBIcarb I make a dry/wet paste of it and scoop some paste to add.

But then you dissolved all and rebased with ammonia and this got you nothing is a weird thing. I have no clue on that.
I suppose re acid-ing and manske is a far cry for finding the hidden THH.

Anyway:
* Nowhere I did a AC run, so I can leave that out now to narrow the variables.
* I have not based yet, will wait til tomorrow to see how much mist appears, to see how much ZnCO3 (allegedly) shows up.
* will think over what base to use, hints welcome. Maybe I better stay in the carb-family and chose sodcarb saturated water instead of cocktailing ammonia?
* will expect some more ZnCO3 to show when basing further, but from there I would bet all my luck on formation of soluble zincate at enough high pH, and let it filter away.
* and oh by the way I had it standing for 2 days and some microwave cooks in between, so all chances for over reacting are exploited :?:

The saga continuous ...

Picture after removing Zn, basing with sodbicarb to 7.5 / 8 (20% layer), filter till water clear, let stand for few hours to see ZnCO3 appearing. It made a gel-ish layer at the top, second picture when that layer is stirred trough.

 

[An1cca]

Yep Jees, I totally agree with your conclusion: use only dissolved carbonate (it is very soluble after all). Also, to basify now, I suggest you also use carbonate. In this way, we can (hopefully) confirm the possibility of this ammonia-free route.

As for the yield-enigma: it might be that the more other ions are in solution, the less THH will precipitate after basification. I can not explain this, it's just another possibility. VDS diluted his mother liquor with water and got higher yields than my concentrated experiments. Also, in the latest THH-fiasco, a lot of ions were present (from the reaction plus a lot of ammonium acetate from neutralizing the large amount of acetic acid). Just another piece for the puzzle...

 

[DreaMTripper]

This thread gets better and better, amazing photographs, fascinating work I'm learning so much.
Regarding activated charcoal (carbon) I read it has an insane
surface area, according to the wiki..
"Due to its high degree of microporosity, just one gram of activated carbon
has a surface area in excess of 3,000 m2 (32,000 sq ft).."
Now maybe not the surface area is suspect for retaining the alkaloids but
could it be its porosity? Or maybe the adsorption qualities could be the likelier
candidate? Adsorption - Wikipedia

The Glove pump was genius Jees! :d

 

[Jees]

I must say I also got suspicious about the AC but then in post #134 & #135 An1cca had a successful (60 mg AC treated !) formation of THH when based all the way with ammonia.
Have you got a yield number of this particular one please?

It would be interesting to compare this yield with the formerly found yield of 87% of post #113 that used only 30 mg AC instead:

... As I said yesterday, I would do a charcoal-purification on the brownish THH from the Manske above. Well, after 10 min of boiling with 30mg activated charcoal, filtering and addition of not too much ammonia, the dried precipipate was more fluffy (as I now sees is typical for reasonably pure THH), off white and weighed 1450mg (pic1). Yield: 87%...

* * *

...The Glove pump was genius Jees! :d

Hahaa it was actually a funny experiment slash semi joke, but in the end it did seem to work on a cotton ball. An1cca I do have a vacuum setup though, and a little pump that draws 75% of vacuum, and a refrigerator compressor that drags near complete vacuum.

* * *


Back to business:

so I let the recipient stand over a day and some more mist formed, alleged ZnCO3.
After filtering it trough a piece of kitchen towel, then a cotton swab, solution was clear again. In the picture you see before and after filtering.

There's a serious color difference between this picture and the one of previous post #142, but this is solely result of photographing in artificial light versus real daylight, the white-balance was totally off between the two, in real it did not change color, the real color is more like in this post.

Soon after filtering some new mist started to form. No wonder as after each filtering the pH rises substantially, an effect An1cca and me both experienced. When the sodbicarb was part of it, pH was 7.5. After filtering pH went 8 remember? Now after this filtering here, the pH went 8.4. So no wonder it keeps precipitating the ZnCO3 present.

At least we have debunked the hypothesis that a solid dash of sodbicarb precipitates all ZnCO3, which was indeed the case for a water experiment, but does clearly not apply for an alkaloid mix.
Does this means the sodbicarb treat is obsolete or even adverse? This is not 100% clear to me because I still have to base mine to see results. I do realize An1cca's findings, but something is still puzzling. I tend to separate my 200 ml in 2 x 100 ml, then base one with sodcarb saturated water, the other with ammonia.

BTW my first batch of reduced harmine+DHH mix was based with excess ammonia only. It has given 2 wonderful travel experiences so far, have 230 mg left for a 3rd one later.

I do think that the re appearing mists after filtering really purificate the solution, just check the cotton swab on the picture, the precipitated ZnCO3 (that is normally white) has taken with it some 'dirt'. As said here before, each precip cleans up.
If this is worth the efforts will be seen soon, in the next episode of basing the solution
Will the dark lords of sodbicarb give birth to another mishap in THH paradise?
Or will the angels of the THH-reality save the day and give way to an emmanation of THH in this earthly corner?
Stay tuned ...

 

[An1cca]

I must say I also got suspicious about the AC but then in post #134 & #135 An1cca had a successful (60 mg AC treated !) formation of THH when based all the way with ammonia.
Have you got a yield number of this particular one please?

I don't have the number right here, but the yield was low here, just above 50% if I remember well. I used more AC because I also had more THH dissolved. I aim for around 2% of activated charcoal. I do think there is not much loss in using AC, while the looks of the alkaloids definitely are much cleaner. I hope we can check the reality of this with the help of LC-MS soon. As well, I might just weigh the filtered AC to check...

There's a serious color difference between this picture and the one of previous post #142, but this is solely result of photographing in artificial light versus real daylight, the white-balance was totally off between the two, in real it did not change color, the real color is more like in this post.

I use the manual settings of my camera, where I can calibrate my white belance each time again on a white sheet of paper.

Does this means the sodbicarb treat is obsolete or even adverse? This is not 100% clear to me because I still have to base mine to see results. I do realize An1cca's findings, but something is still puzzling. I tend to separate my 200 ml in 2 x 100 ml, then base one with sodcarb saturated water, the other with ammonia.

Good plan. Looking forward to the results. And even if sodium bicarbonate will not grant us an ammonia-free route, it can still be applied in the separation of co-reduced harmine/DHH. I will take on this experiment again, using ammonia to basify THH from the mother liquor and to separate harmine from the zinc-salts. Will keep you posted...

BTW my first batch of reduced harmine+DHH mix was based with excess ammonia only. It has given 2 wonderful travel experiences so far, have 230 mg left for a 3rd one later.

Do you have a yield of this combined reduction process?

Will the dark lords of sodbicarb give birth to another mishap in THH paradise?
Or will the angels of the THH-reality save the day and give way to an emmanation of THH in this earthly corner?
Stay tuned ...

:d Half-chemist, half-fantasy writer....Jees, it's a pleasure to have you onboard!

 

[An1cca]

Allright guys, harmala chemistry just got weirder: so I tried to do a Manske post-reduction to bypass zinc-precipitation problems. I reacted 1020mg DHH in 20ml of acetic acid 7% and added 1506mg Zn-powder. After 6,5 hours, I microscopically checked the evolution of the process. As we learned before, no more spikes should be visible on the THH-boulders, so pic01 indicates that the reduction is not finished yet. At 9 hours, pic02 confirmed the completeness of reduction. To these more or less 20ml (pic03), I added 20ml of saturated sodium chloride solution (30g/100ml). Immediately, milk-white clouding appeared (pic04). But after a few hours, a remarkeable thing started to happen: red drops of inmiscible liquid start to appear (pic05) :surprised and in the course of a few hours more, they collect in a little red pool on the bottom of the recipient (pic06) . To save the THH, I managed to dissolve the whole thing in about 200ml of diluted vinegar (pic07) and basified with 50ml of ammonia 12%. Luckily, a familiar precipitation started (pic08) that after drying yielded 522mg of THH (pic09).

Conclusion: In this manner, it was not possible to 'Manske' the THH out of a post-reduction solution. As to the nature of the red 'oil': I don't have a clue:? .... I do recognize it from the sodium carbonate fiasco of post #137...

Coming up: testing the bicarbonate harmine-DHH separation protocol from Van Der Sypt's paper and, as a teaser: "the return of the caterpillar" (pic10)

 

[Jees]

I do not have an exact yield of that harmine+DHH mix reduction, but it was a very low yield I remember and actually I cannot point the reason out clearly because I did a very fast run and lost some here and there and everywhere, I just wanted to have results and a lot got lost due eagerness . I did not mind loosing at that moment, I just wanted something clean enough to evaluate in experience.

* * *

So I had that Zn filtered off after reduction of 2 gr DHH, added sodbicarb to 7.5, filtered a few times until pH 8.4, split in 2 halves of each 100ml

Based 1/2 with sodcarb saturated water:
TERROR :shock:
a light brown sticky gum covered everything, and some snow white precipitates floated in the liquid. So I also got the sticky yellow brown goo, see picture. Had to use methanol to clean the pH probe.
I did filter off the whites that did not get glued on the goo, and washed them, gave 465 mg from 1 gr of DHH. Tasted slightly harmala-like. I thought it might have been a mix of THH + ZnCO3, so I redissolved in vinegar and dashed ammonia 12% on it in an attempt to get rid of the ZnCO3, but the terrifying goo formed again and this time under ammonia. Giving it some time and a heat bath then the ammonia was able to dissolve like 50% of the brown-yellow goo, so it must have been related to ZnCO3 for sure. I counted it a loss, no, actually we have a winner by knowing what NOT to do :thumb_up:

* * *

The other 100ml got based with ammonia:
Now this looked much better, only pale precipitates and no goo. The liquid got a slight yellow hue which I ascribed to the ammonia successfully liquifying the ZnCO3. Easy filtering, washing, got 565 mg of very strongly tasting like harmalas. Low yield indeed, we need to work on that.

* * *

- The combination of first sodbicarb and then sodcarb is a true disaster, twice confirmed by now. Even vinegar then ammonia could not rectify this situation anymore.

- The combination of first sodbicarb and then ammonia is possible, yet we must ask if it is really profitable to do the sodbicarb at all. When examining the precipitates of the sodbicarb treat, and really trying hard to dissolve all sodbicarb out of that (by majorly washing it with plenty of warm/hot water) then yes a lot of ZnCO3 was taken out in that phase. Question: should we? (while we know a full ammonia route works too?).
A first sodbicarb start to look like an option: to have it as a general cleaning step and harmine catcher, but for this last it is not thaaat obvious. To get your harmine out on this point you want like pH 7.5 and then you need to really meter pH (forget the visual clues like 10% rule you need much more than that) and washing out the mother liquid of all that undissolved sodbicarb. It's doable for sure, but not super convenient in my eyes.

To be honest, for a mix of harmine+DHH, then doing a sodbicarb to catch/harvest that harmine fraction, it would require efforts to separate the harmine (recuperation of harmine) from the ZnCO3, while the efforts to separate harmine from DHH far in advance looks much less stressing.
Meaning: using a sodbicarb to really harvest bulk of harmine (after reduction) is not the most fluent practice since there are easier routes.
So if I had a harmine+DHH mix to reduce, I would reduce them both together and harvest them both together. Separating them afterwards is also possible at wish. But I would steer away from a situation that creates {bulk harmine + bulk ZnCO3 + bulk undissolved sodbicarb}.

- The dream of an ammonia free route seems to narrow down to a full sodcarb all the way, we have not tested this yet.

 

[Jees]

Thank you for the THH manske trial, very interesting, and yes there's something "brown" that is lurking around the corner and we get confronted with it in certain situations.
A brown zinc related spook :twisted:

 

[An1cca]

Well Jees, it seems we went through the same situations and emotions :d

Nevertheless I think we're doing a good job at finding a convenient foolproof way by, as you mentioned, eliminating all other possibilities:lol:

I did manage to redissolve the sticky goo in vinegar and, when diluted enough, was able to get some THH back out.

I'm currently reducing a harmine+DHH mixture to check if bicarbonate can be helpful here...

Keep up the good work:thumb_up:

 

[Jees]

...I'm currently reducing a harmine+DHH mixture to check if bicarbonate can be helpful here...

Cool 8)
What criterion will you use to stop adding sodbicarb?
If you're planning to use the sodbicarb as a separator for bulk harmine I'm very curious how that goes. And how you would recuperate the harmine out of all that ZnCO3 and undissolved sodbicarb.

BTW vinegar was not able to clean my pH probe nor was ammonia, methanol did.

 

[An1cca]

Jees, I will strictly adhere to Van Der Sypt's protocol of experiment 2.7.

That way, we can compare yields as well...

 

[Intezam]

I added 20ml of saturated sodium chloride solution (30g/100ml).

What is the function of the saturated salt solution at this step? We already wondered about the salt use when we was reading the VDS paper...



edit: could these red drops be something that's originated from within the salt?

 

[An1cca]

The idea was to recrystallize the THH as the hydrochloride, leaving behind the zinc salts. Given the success in acetate-only solutions (see previous posts), I thought it was worth a try. The red goo/oil is inherent to the harmala's. See post from Jees where he only based with carbonate. However, in sodium chloride environment, there's no goo but oil instead. Not that this helps much:thumb_dow

 

[Intezam]

The idea was to recrystallize the THH as the hydrochloride, leaving behind the zinc salts. Given the success in acetate-only solutions (see previous posts), I thought it was worth a try. The red goo/oil is inherent to the harmala's. See post from Jees where he only based with carbonate. However, in sodium chloride environment, there's no goo but oil instead. Not that this helps much

Thank you An1cca :thumb_up:

 

[ijahdan]

An1cca, I thought you had successfully performed a manske on a solution containing thh before, with just some brown impurities present? Cant remember which post now, thread's getting long!

Anyway, just wondered what was different this time. Did you not bring to the boil and let cool? Did any hydrochlorides form?

Also, could the red oil be 'harmala red' which is sometimes formed in alcohol extractions of syrian rue?

Sorry for so many questions. Ive ordered some zinc powder so will soon be able to start experimenting myself and join the party.

EDIT; I found your post about the previous manske. Post 112. Looking at the pictures, the brown impuritues at the bottom do look a bit dark red coloured. Maybe the same red oil, mixed with other impurities? Whatever it is, the thh hydrochlorides could still be recovered from on top of it, then maybe a second and third manske to see if any more red/brown stuff comes out?

 

[An1cca]

Ijahdan, this time the Manske was done on a post-zinc reduction solution with many other ions (mainly zinc and acetate) present. Before, I Mansked a solution of THH freebase with just enough acid to get it dissolved. For all harmala-freebases, I use about 6ml of acetic acid 7% per gram. Then some demineralized water to make it practical.

Please join the research! Many mysteries remain 'undissolved' ...

 

[Jees]

Jees, I will strictly adhere to Van Der Sypt's protocol of experiment 2.7...

You are very brave to challenge the brown-spook-goo once more, but if VDS did succeed where we did not, it is very important to know why we failed. A first step is indeed to duplicate his claimed success, thank you for that.
Very curious now :thumb_up:

* * *

I had this 1.2 liters of liquid pH 3.3 (citric acid) from 100 gr of exhausted SR seeds. It contained so to speak a max of components, quinazolines and nexine included.
I was about to do some A/B cycles on it to clean it up before my first manske. In this first basing it was impossible to notice any sign of pH depression, nowhere between 3.3 and 12.
At the very best there was a tiny horizontal pH plateau. I've noticed the lack of pH depressions in a total alkaloid soup twice now. I dunno if the large volume is main cause for that, or the massive amount of components. Anyway if you count on pH depressions to separate your components, clean up your goodies well I think. Manskes take out quinazolines et al, while a finalizing pH limit of 9 to 9.5 should eliminate nexine.

 

[An1cca]

Quick fact: activated charcoal does not substantially reduce yields. I dissolved 1058mg of crude THH in 6ml of acetitc acid and 25ml of demineralized water. Then I added 48mg of activated charcoal (Norit powder). I boiled the solution for 10 min and left it to cool for 1 hour. After filtering, I basified the filtrate with 20ml of ammonia 12% and after drying recovered 952mg (=90%) of clearly more white THH. The charcoal that was filtered weighed 70mg (so 22mg were 'caught' ). Given the fact that every precipitation-cycle is lossy, I consider the additional loss acceptable. Certainly because AC is able to clean things up that Manske or basification will not clear. To be integrated in a protocol as an optional step...

 

[An1cca]

Then I decided to check the "separation of harmine-DHH with sodium bicarbonate" protocol. To make a long story short, it's lossy but it works. In line with Van Der Sypt's protocol, I dissolved 1030mg of DHH and 1048mg of harmine in 12ml acetic acid 7% and 40ml of water. To this solution I added 100ml of sodium bicarbonate solution (8g/100ml). At first, nothing happened, but after some stirring, clouding appeared and after a little white, thick precipitation ensued. The solution was left to stand, was stirred some more and then filtered. The filtrate was basified with 20ml of sodium carbonate solution 20g/100ml and, after some standing, the precipitate was filtered.
Then the residue was redissolved like above and the cycle was repeated 6 times (pic01). The seventh time, the filtrate only became a little cloudy and that's where I decided to stop. After drying, 786mg of harmine (75%) and 812mg of DHH (79%) were recovered. They are pretty pure as can be observed from micrscopical images pic02-04.

IMPORTANT NOTE (I will come back on this later on): when working with sodium BIcarbonate, one must make sure all carbonic acid has reacted away. If not, pH-rises occur during filtration or standing, causing incorrect separation. It can be reacted away by time (standing) and/or applying negative pressure (wine-saving pump or other) and/or stirring and/or filtering. Just think of how you would turn sparkling water into non-sparkling water. Heating however is NOT an option because excess bicarbonate can thus be converted to carbonate, strongly influencing pH.