I promised to put on this tek long time ago, but was travelling so here it is. I am a kitchen chemist who does most on feeling so there are no clear amounts added, just the way I do it. Hope it's helpfull and if more detail is required I can post them later when I did another run.

1. Repeat Manske untill you have clear crystals. Mostly it needs about three times. Sometimes the tea is so concentrated that the xtals don't become much cleaner. Then it's advisable to Base the alks out and clean them with cold water till greyish/white. Then do another Manske.

2. In the last Manske, keep the xtals in the filter after filtering and clean your recieving vessel or take a new one. Then slowly pour over cold water till most of it is dissolved. This can be a lot of water. Save this water.

3. Bring the water with the alks to a boil and add a bit of active coal. Keep stirring for about half an hour. Put it on a lower fire so it's just under boiling and let the charcoal sink to the bottom (when boiling it won't sink and charcoal can be hard to filter). Then slowly pour off through a filter.

4. Bring the filtered solution to a boil again and SLOWLY add ammonia. At a certain point small clear needle like xtals will appear. Don't add more ammonia but keep stirring for at least 30 minutes. This will precipitate most of the Harmine. Filter the solution and save your Harmine.

5. Add a bit more of ammonia to get another fraction which will be mostly Harmaline with some Harmine. Filter and save alks.

6. Now you can take your solution from the heat and add more ammonia till all alks crash out. This will be mostly Harmaline. Under a mic you can clearly see the difference with the Harmine. The Harmaline freebase looks pinkish brown and makes flat xtals while the Harmine is needle-like and clear. Filter and save your Harmaline.

7. Dissolve the Harmaline in a solution of H2O and HCl. It may be fairly acidic. When possible do this in a small reflux setup on a magnet stirrer, if not, watch the fumes! It's best to do this in the dark under a blacklight. Add small beads of Zinc while stirring. You will see it react with the HCl and Harmaline. If the reaction stops and there are still zinc beads, add more HCl. If the reaction stops and their are no zinc beads add more of them. Keep doing this till the solution which is first green under the blacklight turns to blue.

8. When blue, put on the light again and filter your solution. Add ammonia till alks fall out. Filter and dry. This (in theory) should be racemic THH.

NOTES: I have no professional way to analyze. In theory the Harmaline should be reduced to THH. Also the color change says something happened. When put under the tongue the effect is way different then the Harmaline. Feels more like Caapi TPA. I would gladly send someone a sample if they can check it for me.

Good Luck!

Awsome! Thanks for this! I just discoverd that ammonia percipitates harmalas better than anything else
I've tried so this may be just what I've been looking to discover.

A cuple questions,

How acidic is 'fairly' acidic? ph4? ph2? ph-2?!
An estimate of the water to muratic acid ratio would be helpful.

Also, will someone on this forum with a formal education in organic chemistry or chemestry or someone who knows enuf about this process
or understands this reaction, regardless of education, please explain what is going on chemically to the layman such as myself?
Does this work?
I undrstand that hydroxide ions are being released and that the zince is a reduction agent, taking up oxygen atoms. That's about as far as my comprehension and knowledge understands this.

Sorry again for my 'unscientific' approach. I guess it would be around ph2-3. Just do your Harmaline in H2O and add HCl till all dissolves. Then add about that amount HCl again and the Zinc. Youll clearly see when it's reacting, all foamy and all. I know that the reaction only takes place ad a certain acidity, but like this it always worked for me. That means: The Green turns Blue. Just play a bit with adding more HCL and Zinc, youll get the feeling soon. When I do it again I will write down exactly the amounts and PH, but that can take a while since I had to break down my setup...

It was a long time ago I was busy with this, but I believe it was based on a TEK by Siddiqui et al but they also didn't have clear amounts written.

Enjoy

All is good, but shouldn't you give at least a theoretical yield of your conversion? The tek done as stated should not (at least in theory) fully convert harmaline to thh. According to Siddiqui et al. the yield is ~50% and increases to ~80 if ammonium chloride is used during the reduction reaction. So you may as well state that this tek only converts 50% of the harmaline to THH, which, in opposition to the threads title are not separated from each other.

Also, it should be reminded that color changes really mean very little, they are misleading and really offer very little information re the desired reactions that may have (or may not!) have happened. Since reaction results based by "color" have been the root of many a misunderstanding and incorrect statements in the past, we may kindly ask for further affirmation of any assertions of this sort.

Since I know that you're willing to taste the product (but don't have the equipment and the know-how!) I will ask whether any willing people could do it for you.

So is there a consensus among the scientifically inclined here as to if this is a viable method to reduce harmaline? I have all the supplies for this tek, and have been skeptical of trying it as of yet, but would love to give it a try if the theory behind it is sound.

Also, i have zinc from buffalo bullion bars lol. Its supposedly %99 zinc so it should work, but is the zinc dissolving in the hcl water, or does it need to be finely cut up as to increase surface area?

And finally, assuming theres only a %50 conversion of harmaline to thh, i assume it would be fairly simple to separate the harmaline/thh via a pka separation like harmine/harmaline, no?

Any help is much appreciated-

yeah, only problem is that we do not know the pka of thh, so...simple in theory, complex in practise.

Well, it would still be worth it to convert some of the harmaline in my rue extract to make it more caapi like, so I'll prob just give it a try when i have some time, and freebase it all out at once. Bio-assaying product before and after reduction to see if it worked.

If the only test you do is bioassay, then do a blind test, because if you expect a change, feeling a change is very likely

I experienced with the ammoniumchloride as well, but since I do not have any means to analyze it I never saw a difference. In effect also not, but thats offcourse just a personal (placebo?) experience.

I know that color isn't a good way to say what happened, but clearly something did. Also I checked that when you add just a tiny amount of Harmaline HCl, the blue quickly goes and it all turns greenish again.

Yield was mostly about 50% of the Harmaline I started with. (I mean, as Infundibulum states the total endproduct, mix of Harmaline and THH)

Also I tested one time to re-x it in Methanol, but had a lot of yield loss. (About 50%) Maybe there is a lot of other stuff coming out of the reaction besides alks?

It made me wonder about 2 things:

1. Where is the rest of the alks I started with, broken down in the reaction?
2. If the solution turns green again so quickly when you add just a bit of Harmaline HCl, why is it so blue if only 50% of the Harmaline reacted? Again, maybe color says nothing, but it made me wonder. Any ideas?

About the Zinc, I prefer beads over powder. The powder makes a quick intense reaction and then you have to add more. The beads slowly (react/dissolve?) away, so you don't have to add new ones all the time and the reaction is more gentle.

About the title, I meant just the seperation of the Harmine not the THH, sorry if thats misleading. I did try to seperate the THH of the Harmaline. I did this the same way you seperate the Harmine from the Harmaline. Boil the solution and add ammonia till alks fall out. Filter and then base out the rest. Seperate portions did come out. But too powdery to clearly see a structural shape and tell a difference. Also it all lighted blue under UV. (For what that helps in info) It also wasn't enough maybe to do this properly.

With respact to #1, I cannot say much; depending on how you do the re-x and whether your impurities are too little or too much, you can lose a fair amount of product. As always yield vs purity are inversely correlated.

As for #2, I see the issue; your assumption is that harmaline fluoresces green, THH fluoresces blue and when green fluorescence turns blue it means that harmaline has turned to THH. Well, since you're extracting and isolating harmalas yourself as opposed to buying high-purity standards from a company, it is wrong to make such assumptions. You really do not know whether harmaline fluoresces green and whether THH fluoresces blue.

With respect to what is happening to the reaction you describe, an alternative explanation is that the harmaline you're using has a yellow impurity, even it minuscule amounts, and that harmaline naturally fluoresces blue. Blue+yellow= green.

The reducing reaction decolors the yellow impurity and lets the blue of the harmaline (and of any THH that might have formed) to shine through. Add back as you describe some of your impure harmaline and it'll get again a green colour. I will say it again here but it is a very important point; we were together with endlessness and the Traveler when we just added zinc powder in just yellow vineger, no alkaloids of any sort (with the yellowiness in the vinegar being an impurity of some sort) and watched it turning clear and transparent.

The point is that reactions can change colours but since you do not know the nature of the colour and you cannot interpret results and putative end-products based solely by colour changes.


You're right about the title, by bad!

BTW, since you could separate two different portions of precipitates as you claim and since it all fluoresced blue, doesn't it confirm an incomplete conversion of harmaline to THH and furtehr support my above explanation with regard to color changes?

Finally, you should not really rely on vaguelly adding ammonia to separate harmine from harmaline (or THH from harmaline for this issus). It has already been calculated that at pH pf 8.75 you get most of the harmine precipitated with the minimal harmaline. And actually, instead of eyeballing ammonia, you can freely add sodium bicarbonate (it wont' get the pH above 8.8 ) to get mostly harmine, then add sodium carbonate (will pH to ~12) to get the harmaline as endlessness has demonstrated. In a tangent, I would even claim that your inconsistent and empirical way of getting the harmaline out of harmaline should tell you something (and something not so good!) about any further experimentation such as its putative conversion to THH. Sorry, but only some rigorous analytical technique will save you here

I see your point with the colors. When I did these tests I checked some THH I got from flowing visions, later I read in a thread that this actually wasn't THH so I knew that the color blue didn't necessarily imply that it was THH. But since theoretically the Harmaline should be reduced to THH and I saw a color change I presumed something happened. I didn't think about a yellow impurity that could also cause that. But it also doesn't mean no reduction took place at all. Allthough my seperating test didn't work out fine, it was a one go with very little amount. And allthough it's no scientific proof, and I agree with Endlessness that if you expect something else you sooner feel that, I did notice a difference in effect and so did other people.

Anyways, I saved some of it and would still be great if someone would have the means to analyze it to make shure. It is a very easy reduction to do and would make it possible for many people to do when no Caapi is available or is too expensive.

Thanks for thinking along!

Oh, by no means I meant that your reduction didn't work! The procedure is simple enough and documented frequently enough to assume that you did do a fair amount of reduction. I am confident that you have THH made from harmaline; the dubious part is the amount of harmaline that got reduced to THH.

I also attach you a paper on fluorescence emission spectra of beta-carbolines. Harmaline basically fluoresces from intense blue to marginally cyan, which further indicates that if your harmaline preparation fluoresces green there is some impurity in it.

As a sidenote, I believe that you can separate harmaline from THH just as you can separate the harmine from harmaline. FV THH was found to be either just harmine or harmine and THH but no or very little harmaline. This is consistent of them using peganum harmala extracts and reducing them with zinc, also incorrectly assuming that harmine will also reduce to THH. I think they were also doing pH-dependent precipitation to get rid of any unreduced harmaline. The end message is that harmine and THH have close or similar pKas and can be co-precipitated.

Even though I see that you'd like an affirmation of your reduction reaction with some chromatographic separation+ analysis, may I suggest you doing a few more things, since since you're in an experimentation binge? This will help gather more data and and generate more meaningful/useful data for the community! So I'd suggest you:

1. do the reduction experiment again, with your harmaline preparation
2. then precipitate THH at @pH=8.75 or by adding sodium bicarbonate
3. then precipitate any unreduced harmaline at pH=12 or by adding excess sodium carbonate
4. Measure and report weights of
a)original harmaline preparation used
b)any THH precipitated @pH=8.75
c)any harmaline precipitated @pH=12.

Samples a, b and c can then be sent for analysis (we'll get to that when you have them ready)

Inf is giving great feeback.. Just one note, when selectively precipitating harmine and harmaline to separate, burnt showed (and this is confirmed in my own preliminary TLC experiments, some more GC-MS to be done in the future) that harmine precipitates reasonably free of harmaline, but the harmaline will still have a significant amount of harmine (of course this all depend on the ratios of harmine:harmaline that are in your rue to begin with, which we cant know beforehand, but generally speaking this will be true...)

So to better isolate harmaline, you should repeat again the process with just your "harmaline", and in this way what precipitates first in your second round will be mostly harmine and what precipitates after will be harmaline reasonably free of harmine (or at least much less than in the first round). Dont know if that made sense...

Thanks for all the great feedback. It sounds like a very good protocol.

Allthough I just finished isolating some Harmaline (Will give it another seperation like Endlessness proposed), I'm out of Zinc, my Ikamag is broke and have little time at the moment to do the reduction. I will get to it as soon as possible though and gladly send the results.

Thank you sir.

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I should add that its quite spectacular to watch the separation of harmalas through a column under UV light.