Harmaline to THH reduction with zinc and vinegar works! (GC-MS results)

[endlessness]

So, small update. Harmine does NOT get reduced to harmaline and THH with zinc, as analysis has show today. Harmine stays intact. So trying to reduce a mixture of harmine/harmaline will leave harmine intact and reduce the harmaline to THH. If you want THH, better do a couple of selective pH precipitations to separate harmine and harmaline, and then use only the harmaline (or 'mostly' harmaline at least).

 

[Infundibulum]

So, small update. Harmine does NOT get reduced to harmaline and THH with zinc, as analysis has show today. Harmine stays intact. So trying to reduce a mixture of harmine/harmaline will leave harmine intact and reduce the harmaline to THH. If you want THH, better do a couple of selective pH precipitations to separate harmine and harmaline, and then use only the harmaline (or 'mostly' harmaline at least).

Sweet, finally some hard data on the issue!

Thanks!

Also, the stuff about sodium zincate is crazy! How did you come with this? It definitely sounds worth trying - however what would also work would be complete neutralisation/acidification of the reaction with HCl or acetic acid, this will convert everything to their respective salts. Then do a Manske - zinc acetate/zinc chloride will stay in solution and can be washed away.

EDIT: ~2 grams of acetic acid will completely react with and convert 1g of zinc to zinc acetate. Using 100ml of 5% vinegar per 1g of zinc used for reduction should, in theory be more than sufficient to do the trick. Ideally one would need enough acid to see everything dissolving.

 

[endlessness]

Thanks inf

The sodium zincate thing, I just came across when searching for "zinc hydroxide solubility".

Regarding the manske, InMotion said he thought zinc chloride would also precipitate when adding salt due to "common ion effect". Nevertheless, in the tests I made yesterday it seemed there was a small amount of precipitates only, those being harmalas. If zinc had precipitated, a lot more stuff would have come through. And indeed when I based the solution after retrieiving the harmala precipitates there was a lot more precipitation, probably the zinc.

Nevertheless this is easy to test and Ill do it this weekend, simply doing a control, by dissolving pure zinc in acidic solution and adding salt to see if anything precipitates

The other question is if THH precipitates well with manske. Im currently extracting some rue, this weekend hope to separate the harmine and harmaline and then be able to test the reduction again and manskeing the precipitates.

 

[endlessness]

Just did a control test, added a bunch if zinc to vinegar, let it stand for a while, filtered off excess zinc, brought it to a boil and added 150g salt per 100ml of solution (somewhat more than manske), and its been standing for hours already and no sign of precipitation.

Meaning, if one does the harmaline-to-thh zinc reduction, one can precipitate with a base the THH, redissolve in warm vinegar, filter off anything undissolved, bring to a boil and add salt to (hopefully) precipitate the THH, and zinc will not precipitate.

Now the only question is redoing this with separated harmaline to know if THH precipitates properly with the manske or if some remains in solution

 

[Crystalito]

Are there any news on harmine/harmaline reduction using magnesium or aluminium? Those metals are easily acquired and could prove usefull...

 

[The Day Tripper]

Just did a control test, added a bunch if zinc to vinegar, let it stand for a while, filtered off excess zinc, brought it to a boil and added 150g salt per 100ml of solution (somewhat more than manske), and its been standing for hours already and no sign of precipitation.

Meaning, if one does the harmaline-to-thh zinc reduction, one can precipitate with a base the THH, redissolve in warm vinegar, filter off anything undissolved, bring to a boil and add salt to (hopefully) precipitate the THH, and zinc will not precipitate.

Now the only question is redoing this with separated harmaline to know if THH precipitates properly with the manske or if some remains in solution

I want to try this, like tomorrow lol. I'm at least deadset on doing a harmine/harmaline separation on some mansked rue hcls, and a vinegar/zinc reduction on the harmaline followed by basification with koh to precipitate the zinc hydroxide & fb thh.

Since zinc chloride, and zinc acetate are both very water soluble, i assume that what causes a manske to precipitate thh hcls, will not cause zinc chloride to precipitate if like thh, the saturation of nacl converts some of the zinc acetate to chloride.

If zinc chloride is formed, and behaves as thh/harmine/harmaline hcl's do in a saturated nacl solution (precipitation) then that ideas not really viable.

this makes me wonder though-

The tetrahydrate ZnCl2(H2O)4 crystallizes from aqueous solutions of zinc chloride

-from zinc chloride wiki.

But maybe that could be useful if you used hcl to dissolve the thh/zinc, then let it suck up h20 until it precipitates as the tetrahydrate. Filter and add salt/manske to get thh hcl. That begs the question though how soluble is zinc chloride tetrahydrate in hcl water? They say it crystalizes out but theres no solubulity given.

As well, if you evaporated your hcl dissolved (non-mansked) zinc/thh, would the tetrahydrate stay hydrated long enough to pull the thh hcl with distilled water without pulling the zinc tetrahydrate as its at least water insoluble to some degree, and fully hydrated?

Finally, if thh hcl is insoluble in dry acetone, then since zinc chloride is very much soluble, you could wash your zinc chloride contaminated thh hcl with acetone to remove the zinc. Zinc chlorides solubility in acetone is 4300g/l. It would take ~3 5ml tone washes at most i assume to get the zinc chloride out.

Can anyone elaborate on thh hcl's solubility in dry acetone? Or even harmine/harmaline hcl's for that matter?

If they're insoluble (harmala hcl's) in dry tone then it seems like the easiest way to wash away the zinc is a few tone washes. After doing your reduction and basifying @ ph 12, Just take your precipitated thh fb/zinc hydroxide and dissolve it in dilute hcl water and evap. Wash a few times with minimal dry tone and it should pull out any zinc chloride. No problem with knowing if thh will precipitate in a manske as its not being done, but not knowing the solubility of thh hcl in dry acetone could make this unfeasible. If zinc chloride tetrahydrate is insoluble in dry acetone this won't work either. And from what i understand, dissolving the zinc hydroxide in hcl water would hydrate the zinc chloride, correct?

Bit of a ramble :lol:, but theres some new approaches in there that may be of relevance and any observations or criticisms are welcome.

 

[tryptographer]

Since zinc chloride, and zinc acetate are both very water soluble, i assume that what causes a manske to precipitate thh hcls, will not cause zinc chloride to precipitate if like thh, the saturation of nacl converts some of the zinc acetate to chloride.

You lost me there
Isn'it all about the concentration of the Cl- ions, it doesn't matter if the cation is zinc or sodium...?

Anyway, I want to test this harmaline reduction with magnesium instead of zinc or aluminium. I have some magnesium powder that's been in the family for decades - it's time to do its job

But how to know if it succeeded??? Is there any low-tech analysis to detect the difference between THH and harmaline (besides bio-assay)? UV?

 

[alkan0id]

So has anyone made any advances with this, conclusive or otherwise? It would surely be a landmark achievement to nail down a tek to turn harmaline into THH so easily.

A lot of thought has been put into the pitfalls of using zinc, and possible ways of removing zinc compounds from the final product. Has anyone investigated to see if it might be easier (or not) to use aluminium or magnesium? I'm a chemistry dunce myself, but presumably using a different reducing agent would present different problems and hence more opportunities to finding a solution.

This has been a really interesting thread to read, thanks to all.

 

[Phytonaut]

Hi,

I see it has allready been asked, but what about the isomers of THH?

Any way to end up with only the active form? I read that the isomers change in boiling water, but not sure what changes to what...

Thx

 

[alkan0id]

OK, I think this might be a way to do it. Please bear in mind I have NO education in chemistry, so the following steps I suggest here are in part based on ASSUMPTIONS. I'd be grateful if anyone with a better knowledge of chemistry could point out any errors or omissions. The idea is to use Al as the reducing agent, since aluminium hydroxide is soluble in excess NaOH, as demonstrated here:

Al is also a stronger reducing agent than zinc, meaning that it might just be able to reduce harmine to harmaline as well. If this is the case, then theoretically there would be no need to perform the harmaline purification step - you could just dump a rue extraction into the mix wholesale.

1) Take elemental aluminium shavings or dust, and add to glass container of 5% acetic acid (distilled vinegar), and your reasonably purified harmaline.

2) Stir for a couple of hours, in a well ventilated area to get rid of the hydrogen gas.

3) Filter out the leftover aluminum dust/shavings.

4) Pour in NaOH solution to excess, to base out the (presumably) THH acetate and dissolve the Al(OH)2.

5) Filter and thoroughly wash the THH freebase with water.

What you're left with should presumably be pretty pure THH, leaving the valid question of which isomer(s), and in what proportion, you have. Quoting from this thread: THH isomers - Synthetic and Natural THH differences? - Plant Analysis and Substance Testing - Welcome to the DMT-Nexus :

THH has 1 asymmetric carbon atom (position 1 in the beta carboline moiety) and its synthesis reduction from harmaline is not preferential to either, so the end-product is a 50:50 mixture of both stereoisomers.

I seem to remember reading somewhere that boiling converts the less active isomer into the more active one, leading some to theorise that brews that have been boiled for longer are more potent. Which one of D and L is most potent, I don't know.

 

[endlessness]

In theory adding excess sodium hydroxide will also make zinc soluble in the solution (I think I wrote it in this thread sometime ago?), but more tests have to be made

Before actually doing this aluminium test, you shoudl try to do a control without any THH, and see if you can get aluminium to become soluble in solution with excess sodium hydroxide. If so, then its good indication and one can try with harmalas.

 

[alkan0id]

Yep, somewhere you (or someone else) mentioned that excess NaOH should turn insoluble zinc carbonate into soluble sodium zincate, which has yet to be put to the test (on the record, at least). But with the aluminium method, we know for sure that aluminium hydroxide is soluble in excess NaOH. It's also a stronger reducing agent than zinc which opens up the possibility that it can reduce harmine as well as harmaline, which would be a really nice bonus. I am, of course, blindly assuming that the elemental aluminium in the acetic acid solution will form aluminium acetate, which will then react with the NaOH to form aluminium hydroxide, which is then made soluble in yet more NaOH, theoretically leaving us with only THH freebase.

Assuming I have some kitchen foil that is 100% aluminium with no dodgy chemicals in it (doubtful?), I could give this a shot. I think I might have to order some pure Al granules though, I don't trust kitchen foil. Obviously i don't have a mass spectrometer to hand, and I'm not really in a position to bioassay since I'm currently on St. John's Wort which I was advised not to mix with harmalas. I can't imagine THH is much less contraindicated with SJW than harmine and harmaline are, despite not being an MAOI.

 

[alkan0id]

Before actually doing this aluminium test, you shoudl try to do a control without any THH, and see if you can get aluminium to become soluble in solution with excess sodium hydroxide. If so, then its good indication and one can try with harmalas.

Good idea. Such a control would also show me how much excess NaOH is needed to fully dissolve the Al(OH)3. If I tried it with the harmalas straight away I'd have no idea how much of the precipitate was what.

 

[alkan0id]

Ah, it turns out that adding excess NaOH to Al(OH)3 doesn't so much "make the aluminium hydroxide soluble", as it reacts with it to form sodium aluminate, so this would be analogous to the excess NaOH turning zinc hydroxide into sodium zincate. This works because both zinc hydroxide and aluminium hydroxide are amphoteric compounds, so the excess NaOH causes them to behave as acids, reacting with them to give us soluble salts. So zinc and aluminium look like absolute winners for this reduction tek, provided that NaOH is used as the base, not sodium carbonate. The amphoterism of the hydroxides of zinc and aluminium are the key to making this work, meaning that magnesium is no good for this, since magnesium hydroxide is not amphoteric, giving us no magic way of "making" it soluble. It would be really nice if aluminium was strong enough to reduce harmine to harmaline (and therefore THH).

 

[endlessness]

Sounds promissing, let's test it

If nobody does, in about a month from now I will have time to do these things again

 

[The Day Tripper]

Ah, it turns out that adding excess NaOH to Al(OH)3 doesn't so much "make the aluminium hydroxide soluble", as it reacts with it to form sodium aluminate, so this would be analogous to the excess NaOH turning zinc hydroxide into sodium zincate. This works because both zinc hydroxide and aluminium hydroxide are amphoteric compounds, so the excess NaOH causes them to behave as acids, reacting with them to give us soluble salts. So zinc and aluminium look like absolute winners for this reduction tek, provided that NaOH is used as the base, not sodium carbonate. The amphoterism of the hydroxides of zinc and aluminium are the key to making this work, meaning that magnesium is no good for this, since magnesium hydroxide is not amphoteric, giving us no magic way of "making" it soluble. It would be really nice if aluminium was strong enough to reduce harmine to harmaline (and therefore THH).

What about potassium hydroxide?

Would it work as well as sodium hydroxide?

Thanks-

 

[alkan0id]

What about potassium hydroxide?

Would it work as well as sodium hydroxide?

I'm no chemist, but it looks like it would work, since potassium zincate and potassium aluminate both exist. Since KOH is a strong base, and Al(OH)3 is amphoteric, these should react to form a soluble salt, leaving only THH f/b to filter and wash. I could test, but I don't have pure aluminium or zinc to hand, and am unsure what undesirable chemicals might be lurking in kitchen foil that might react with the acetic acid and produce all kinds of nasties.

 

[alkan0id]

Have had 0.2g of finely cut kitchen foil soaking in 50ml 5% acetic acid solution at room temperature for almost 24 hours now, with no sign of any hydrogen bubbles. Has anyone else tried this? Do I need to heat the vinegar first? Presumably I need the aluminium to react with the vinegar in order for it to reduce harmaline.

 

[endlessness]

With zinc, the bubbles were pretty small, wasn't easy to see at first...

Hard to say, though, Ive never worked with aluminium as reducing agent before, to know how well it works.

Please be careful with hydrogen gas explosions, by the way. Dont close container tightly, and be careful with flames

 

[alkan0id]

Al has a reduction potential of -1.66V, compared to Zn, which has a reduction potential of -0.76V. If I understand correctly, lower is stronger, so Al should be more than twice as strong as Zn, hence my optimism that it might be able to reduce harmine as well as harmaline. It could be that I need to use fine aluminium powder instead of chopped up foil, but someone earlier in the thread found that they did get chopped foil to react with vinegar, it just took longer than with finely shredded foil. I have left the top off the vinegar bottle to prevent gas buildup, although it really doesn't look like any gas is being formed. That said, I don't really know for sure. There appears to be no change after over 24 hours.