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

[An1cca]

Those are just gorgeous! :want:
Looking forward to see what the reduction does to these beauties

 

[Jees]

It is reducing :surprised

After 2 hours (mostly standing, few swirls) the longitudinal axis remains strong but all feather is gone.

Then, these monodimentionals like to construct 'spiders'.
These are 2 of An1cca's pictures when he was at that stage, if may use this as a reference for what reducing looks like:

And in attachment: first, the feathers got stripped, then they like to make spiders.
Then yes it's like An1cca's pictures very much.

I've not checked since.

This suggests an upper pH layer of harmaline after all?

 

[Jees]

We're now 10 hours further, and the spiders traded for the THH bolster works.
Must re examine that failed first Zn reduction attempt. And also that pH thing around DHH.

 

[An1cca]

That looks like THH for sure.... Well, no Nobel-prize for the Nexine after all :lol: . But, 1 mystery solved! Good work and nice pictures, your setup is really good.

I'm planning on packing the samples again this evening...I'm gonna put them in a plain envelope now, with the address of someone who might exist and tracking option!

 

[An1cca]

So, I repacked the samples and they're ready to be sent tomorrow. Only from sample #5 I had nothing left.

sample N°: Description
#1: Harmine from pH-metric separation following VDS-protocol 2.3
#2: Harmine isolated by bicarbonate-separation following VDS-protocol 2.4 (post #160)
Note: the influence of decomposed carbonic acid wasn't known then, this might have led to some DHH-contamination
#3: Harmine from HAR-DHH to HAR-THH conversion (post #169): Na2CO3 as base
#4: Harmine from HAR-DHH to HAR-THH conversion (post #169): NH4OH as base
#5: DHH isolated by bicarbonate-separation following VDS-protocol 2.4 (post #160)
Note: the influence of decomposed carbonic acid wasn't known then, this might have led to some DHH-contamination. Also, I accidentally used practically all of it for further pH-metric purification, hence the very small amount.
#6: DHH from #5 after removal of first-precipitating fraction. Presumably quite pure DHH.
#7: THH from last higher-yield DHH-conversion (post #177)
#8: THH Activated charcoal clean-up (post #159)
#9: THH from HAR-DHH to HAR-THH conversion (post #169): Na2CO3 as base
#10: THH from HAR-DHH to HAR-THH conversion (post #169): NH4OH as base

I call on mother Aya to protect the letter and to guide it to the hands of our beloved receiver that will take away all remaining doubts concerning VDS's protocols. May you both be blessed ...

 

[Jees]

^^^ Amen to that

Maybe Nexine can still apply for the Nobel Prize of sexiest illusion

* * *

I have some photos to share of the resulting THH.
EDIT:
Total reaction time 20 hours, mostly standing, few swirls, weight yield 80% ! I consider the good yield as result of basing with ammonia til 10, then I thought there was still some ready to precipitate (yellow) and continued with lye, needed only very little to push to 12. The ammonia took good care of the Zn salts --> zincate , then going further with lye seems OK to do.
Zn-mist as expected to form at 7 and disappeared at 9 under the ammonia. THH crystals started to form from above 9. Reaction time was on top of a heater radiator most of the time meaning around or just above 40 - 50 deg C (100 - 122 deg F).
Washed the product with sodcarbed water before drying.

 

[Jees]

So how did Nexine come to "exist" in our minds?
We have to go back to post #120

Thank you for paving the way, I'll be in your footsteps

* * *

I've been mentioning this:

Hmmm, when I rise to pH9 then there is still a lot of yellow in the 'milk'. Only when rising to at least 11.5 then all yellow start becomming white, usually I rise to just above 12. I've always thought that this yellow (above pH 9) is the harmaline (DHH) that was not readily precipated as FB.

Because we had a theoretical outline of calculated estimations here

...The intersection point corresponds at a pH of around 8.75, which is the pH where one will get the most harmine with the least harmaline contamination. At this pH one will in theory get at around 92% harmine and 8% harmaline in his precipitates. ...

So I was always thinking that whatever drops out above 8.75 must be the harmaline, it fitted so nicely the calculated estimations.

So I took a better look at what exactly drops out above 8.75.
After having the harmine & harmaline filtered out as in previous post, I continued to rise pH to near 11 with lye water (I was sure lye would not precipitate). I did harvest 400mg of dry product. What is it? Characteristics:
- nice beautiful yellow liquid until it FB as white-ish;
- start of precipitation from 9 (then a first mist appeared);
- from 10.5 and above most or all yellow has gone white FB;
- FB in the water more gell-ish, no hard structure like harmine and DHH;
- more difficult to filter than harmine & DHH, because of gell type;
- some just went trough the filter leaving the filtrate misty;
- no pH depression noticed for this precititate;
- it all came along with 2 X manskes, it seems to survive manske.

I have this product because I always base my extracts till 12. VDS only worked upto 9.6 which explains he had nothing noticed above 8.5.

I had some of that product already submitted to vinegar and Zn for 3 days now, and no color change at all, see picture before reduction attempt and after 3 days. So I believe it is no harmaline. And the blacklight color indicate (don't you think?) it is also no natural level of seeds-THH that I gained.

Whatever it is (and I thought it was the strict harmaline for years), I doubt it can serve us when we're on a harmine, harmaline, THH hunt.
Next time, when I do A/B's on syrian rue, I'll limit the highest pH to 9.00 to cut out this portion of whatever it is. All hints welcome.

* VDS was quite bold stating that harmaline (DHH) would not be found higher precipitating than pH 8.5 - 9, he even called some media wrong (mentioning Nexus for one). Now, so much further, I agree and I don't. I think that under certain conditions he is right, under other conditions he is wrong. As I think of it now: if the conditions permit pH depressions to take place, DHH will fall out much sooner as when the conditions obstruct the pH depressions to occur.
I've had experiments in non-VDS conditions where the pH depressions were absent, in these cases the pH curves as shown in post #120 are not to be neglected, and harmaline can continue to precipitate at pH levels as high as 10 to 11. I think the DHH that precipitates under these higher pH's has let to believe in Nexine, but nothing different than DHH that formed under a higher pH regime. We have seen how vulnerable crystal forming is, shape-shifting according to its changing chemical surrounding. Certainly not dried, but in situ crystals uncovered the unmistakable commonality, the feathers and cross.

* The one experiment where Nexine did not seem to reduce: only absent of color change was used as a means to conclude 'no reducing'. But at that time no check on crystals was done under microscope. Was the concentration too low to have a color change? This really has set us on a wrong foot and I must take responsibility for that one and I still wonder what happened. An error of mine? Possible but I would really hate that.

* I must learn to do tests twice at least before coming to a (premature) conclusion. Or having done tests by different people and ending the same, like when we had when reducing harmaline. In this light I must re-check the [strong base --> no-pH-depressions] observation again.

Results: I will no longer try to avoid Nexine by moderating pH on soups of syrian rue. In the stages of impurities the pH depressions will not show up anyhow (according to repeated findings so far). The soups will be pH 11 at least as the curves of post #120 indicate the last of DHH to potentially crash out there, confirmed by yellow --> white.
My recent batch however had only seen pH10 max, I'm curious.

* * *

TUV is another animal as it's face (photographs) is distinct. But which ones were? It were those vessel crystalized and obtained with salt contamination from a previous manske. Normally we do not end manske but A/B + washing as per VDS.
As soons as a few A/B's were done, and thus salt contam lessened, it's pH behavior tumbled down from 8.4 to 7 as a pH starting depression point. And at same time its in-situ crystals began to resemble more and more harmine.

* * *

With this I would like to bury Nexine and TUV as experimental shadow games, born out of (righteous but) incomplete intel. I think VDS paper should not pretend to be complete but to be correct only in the conditions as put in the paper.
I hope to not see TUV & friends again in the future, becoming better as we go.

Any remark/thoughts very welcome.
BTW ijahdan I hope you're still with us?

 

[An1cca]

The rise and fall of the mystery alkaloids... :d Excellent round-up on these two special guests, Jees.
I totally agree concerning VDS's somewhat pretentious claims about him being right and us, Nexians, being 'wrong'. It's all a matter of starting material and methodology. It does seem that he followed the route of purity though, something a purist like me tends to appreciate8) .
I think your conclusions should be integrated in the comprehensive yet simple tek-to-come.
BTW, samples are on their way, can't wait for the LC/MS results.. :want:

 

[Intezam]

... samples are on their way, can't wait for the LC/MS results.. :want:

8) :thumb_up: Yeah, can't wait too....this is really exciting

 

[An1cca]

Hey guys, as a sidenote I tried an alternative way of recrystallizing our beloved alkaloids. You can see the setup in pic01 and pic03: a beaker with dissolved alkaloid (water + minimal amount of vinegar) is placed within a larger beaker in which ammonia solution 3% is poured. Then, the larger beaker is sealed. The idea is to let the ammonia diffuse into the solution, hereby slowly recrystallizing the alkaloid. The first experiments quickly showed that even dilute ammonia would immediately start to precipitate alkaloid at the surface and allow too little time to produce large crystals. So I decided to put a layer of Al-foil onto the smaller beaker and just punch some holes through it. That seemed to do the trick! Pic01 and pic02 show the longest harmine-needles I've ever seen.
And then for DHH...pic03 and pic04 show the ferns we've come to know at the microscopical level in real life:shock: ! So in this way, the crystals can also show their 'true face'. Perhaps we might even have a crystal caterpillar crowling around when precipitating HAR/DHH 50/50 ?
I also added another picture of sublimated THH (pic05). Heating was applied using a soldering iron in an improvised vacuum setup. Unfortunately, the surrounding glass recipient imploded during the experiment. Be careful guys! I hope we will find out that our precipitated THH is pure enough to make such sublimations mere academic 'spielerei'. Pic06 finally shows the beauty of THH.HCl after Manske. The 'crystal sky' that formed at the surface came to crash upon the bottom layer of THH-urchins...

 

[pitubo]

Stunning pictures An1cca!

 

[Jees]

Absolutely brilliant.

And the vape thingy was in the pipeline for some time, you nailed a practical solution to it.
We've seen this happening before on a microscope glass, when a drop of ammonia was placed aside a alkaloid drop, before merging the drops. It only waited for an An1cca hands down interception :twisted:

Very cool results

Btw a trusted and informed Chinese volunteer essayed 150mg harmine + 150mg THH + 50 light
Boot in the face and a little of the slap too, very intense.

 

[Jees]

It looks like it could replace 'control of substance by microscope'.
I could not have imagined this fantastic result.
:thumb_up:

The question-myth "Will THH manske?" could not be more impressively answered.
(given positive ID's)

 

[ijahdan]

Been offline awhile. Just caught up with the latest pictures. Really cool, seeing those familiar crystal shapes grown to such a size. Ill try this ammonia slow infusion and see if I can get something similar, as I still dont have a microscope.

I havent had time to do another reduction but have got what looks like fairly pure harmaline ready to go. Hopefully over christmas holidays there will be more time and by then maybe the results of an1cca's samples will be through too.

Great stuff!

 

[exquisitus]

An1cca, how much rue does one need to get to those pictures? 1 kg?
waiting for the tech holding my breath

 

[Jees]

...Ill try this ammonia slow infusion and see if I can get something similar, as I still dont have a microscope...

Maybe this vape basing style can make microscope completely obsolete. Microscope needs a learning curve too. Mine is a 100 euro thing and a pleasant toy but there are moments of failure/grrr too.

For a tek and for myself, I stick to ammonia for now, so simple to work with. Because any carbonate on vinegar produces CO2 (see pics) for which VDS and An1cca warned about, and bicarbonate makes twice as much CO2 than carbonate (if I'm not mistaken). Foaming is nice and looks great, but the extra care and waiting for the CO2 effects to subside, and CO2 plays the pH too, then ammonia cuts that corner completely.

For washing products I think water + a pinch sodium carbonate is worth gold.
Not a real concern here, but it eliminates the hygroscopic feat of ammonia in the drying phase.

 

[An1cca]

An1cca, how much rue does one need to get to those pictures? 1 kg?

Exquisitus, for this experiment, I dissolved about 500mg of harmine or DHH in 75ml of water (+3ml of vinegar 7%). It takes about 2 days to get to the pictures in my previous post. Yield of harmine+DHH freebases from rue is about 2-4% dry weight. Check out the OP article. I tried to do the same with THH, but it had a hard time crystallizing and turned into a dark debris (oxidation?)

Jees, I still would recommend microscopy for ID'ing: 2 minutes vs 2 days; 0,2 mg vs 200mg....But yeah, the crystals are just beautiful !

 

[Jees]

Didn't realize it was 2 days
Anyway it's such a great add.

After a while working with the archetypes they become easier to notice, here harmine and a dash of harmaline.
8)

 

[An1cca]

Didn't realize it was 2 days

Perhaps the crystals can be generated somewhat quicker. It's all a question of how many and how big the holes are you make in the Al-foil. I might have erred on the slow side here ...

After a while working with the archetypes they become easier to notice, here harmine and a dash of harmaline.

Won't you consider taking a short break from the microscopy, Jees ?

 

[Jees]

...Won't you consider taking a short break from the microscopy, Jees ?

Oh no Sir :lol:

I had a new batch of Rue preparation, started with 200 gr seeds. There were at least 5 boils and squeezing the seeds out to hand-dry each wash. A few A/B's, then a ton of manskes, then 2 charcoal boils, another manske or two.
Used to get 5 to 6 % yield but with all these cleanups it comes to 4% freebase alks.
This time I get a nice 50% harmine & 50% DHH.

Here's some vessel crystals of the very first solids formed during the very first pH depression. The beams with split ends resemble the TUV pics, we consider it now one of harmine's faces. The beams start to play into stars, and then the classic needle face of harmine appears also. This is not in-situ and thus crystals have a more free way of expressing themselves.