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

[InMotion]

last edit - Personally I wouldn't use carbonate as a source of base. I'd stick to the procedure and use ammonium chloride and ammonia to form I presume the zinc amine complex(which I thought the haulting of precipitation was governed by equilibria before). Or maybe toy with only using NH4Cl(or similar ammonium salt) and a base such as NaOH running the reaction 'dry' to see if the precipitate went into solution or not. I try not to work with weak acids in conjunction with weak bases though I understand the desire to do so, due to ready availability.

In my second post I was assuming that Na2CO3 would form less of the Zn(OH)2, which was based on absolutely nothing. Hydroxide is likely a good friend in this instance.

It is interesting that the results were so clean using house-hold vinegar as the acid. If only I could remember my qualitative analysis lab's :lol:.

I'll look into the high pH value thing, I don't see an obvious reason for instability off of the top of my head.

It would also be good to know if THH will precipitate in a saturated NaCl solution(ala 'manske').

 

[Infundibulum]

last edit - Personally I wouldn't use carbonate as a source of base. I'd stick to the procedure and use ammonium chloride and ammonia to form I presume the zinc amine complex(which I thought the haulting of precipitation was governed by equilibria before). Or maybe toy with only using NH4Cl(or similar ammonium salt) and a base such as NaOH running the reaction 'dry' to see if the precipitate went into solution or not. I try not to work with weak acids in conjunction with weak bases though I understand the desire to do so, due to ready availability.

Well, yeah, the "classical" method definitely works, the idea working with vinegar and sodium carbonate was based on that household store-bought items can be used for the conversion in a manner that's easy for pretty much everyone. The more people can do it the more accurate information we get about THH.

It would also be good to know if THH will precipitate in a saturated NaCl solution(ala 'manske').

Genious!

How didn't we think of that already? Endlessnes, take notes! reduction with zinc and vinegar, the products are zinc powder, zinc acetate, and THH acetate; filter the solution, zinc goes away; add kilos of table salt, THH hydrochloride precipitates and is collected, zinc acetate goes away!

 

[endlessness]

Thanks for the feedback, everybody!

The NaCl precipitation idea is a good one. But then it makes me wonder: What is it about a molecule that makes it precipitate in a NaCl saturated solution but others not? What is it about vasicine and vasicinone and their molecular structure that prevents their HCl form from precipitating in those solutions? Not exactly related but curiosity: Would DMT for example precipitate in salt saturated solutions?

Lastly, yeah Ill def research this but god damn it guys you all give too many interesting possibilities to research and im a poor bastard with already another full time job :lol:

 

[nen888]

..i'm wondering if the THH isomer thing has been taken into account..i posted the full text of this comment from Jace Callaway in Entheogen Review 1995 in the acacia thread [p.15 bottom]:

"I have tried THH, alone and in combination with MAOI, and there is a twinkling of sorts, but one might get a substantially similar reaction from Prozac. Also, there are two isomers possible from THH (+ and -, or d and l). I would suppose that one is more active than the other. Simply heating in boiling water will convert one to the other, so most teas will have both. the “d” form is the one reported to be found in the plant (d-leptaflorine), and I have often wondered about tales from the rainforests, where the tea is sometimes prepared just from soaking the macerated vine overnight (no heating, no admixtures), with visions resulting. Note: I suppose the desired vine should be a chemovare having high levels of THH.

"Calliandra pentandra has good amounts of THH in the leaves, and it is used as an add mixture by some groups like the Shuar in Equador, and visions have been reported by reliable western folk from this and Banisteriopsis caapi. So, there still may be something there to look at more closely.

.

 

[Crystalito]

I tried some things with aluminium and vinegar.

Four vessels were prepared:

1) Small pieces of aluminium foil, room temperature vinegar
2) Small pieces of aluminium foil blenderized*, room-temperature vinegar
3) Small pieces of aluminium foil, hot vinegar ("boiled" in ben mari)
4) Small pieces of aluminium foil blenderized*, hot vinegar ("boiled" in ben mari)

Results (aka Captain Obvious to the rescue)
Aluminium reacts with vinegar, with vessel 4 being more vigorous (heat-large surface). 3 and 2 were almost on par, with 3 starting sooner. 1 was the last to react.

It takes some time but as the reaction progresses it happens more vigorously in all cases. An explanation for this might be that the acid first reacts with the metal oxide, and when this is consumed then the acid is left to react with the more reactive metal underneath.

More or less nothing new here, standard acid + metal reaction "as seen in the literature" - just confirming the "obvious".


* Be careful!!!!! Just in case the blender used is not to be used on food items, its only used in projects and wahed thoroughly after this application. Small pieces of aluminium foil were used, and it was done in pulses. In some instances there were sparks from the metal so beware. Blenderization was carried outside, behind protective shield and the hand used to operate the mixer had thick glove on. Careful not to breath dust generated! The experimenter might have been overly cautious and/or paranoid.

 

[benzyme]

What is it about a molecule that makes it precipitate in a NaCl saturated solution but others not?

electrostatic vs. van der waals interactions.
this is the basis behind ion exchange chromatography, where bound analytes are displaced from the charged functional groups of ion-exchange resin by changing either the pH or salt concentration, or both. and yes, DMT can be precipitated with a high enough salt concentration, assuming it's in free base form where the net charge is zero, because the overall molecule has predominantly van der waals interactions (it's mostly hydrophobic)

 

[endlessness]

Thanks benz, some more key concepts to research!

So whats your take, considering electrostatic and van der waals interactions, would THH precipitate in a salt saturated solution>?

Crystalito, thanks a lot for that post! Seems alu foil would work too then, but yeah indeed we gotta always be careful with metal contamination and all of that

 

[benzyme]

So whats your take, considering electrostatic and van der waals interactions, would THH precipitate in a salt saturated solution>?

at net neutral charge, yes. it has one more H-bond donor and H-bond acceptor than DMT, so it may require more salt to precipitate it; it's a more polar molecule.

 

[Hyperdimensional Cuttlefish]

I am pretty excited about this. If effectively separating the zinc or aluminum (or whatever reductant used) is possible with household stuff, I will jump on this ASAP. My chemistry is too rusty to figure that out on my own, so I will just implement whatever you guys come up with.


Got about 25+grams of harmala freebase, and several pounds of peganum seeds sitting on the shelf waiting at the starting gates! VROOOM VROOOOOM!!!

 

[tripwire]

Has anyone tried doing the manske with this yet to remove the metallic compounds?

If not, i may try it myself. As I'm no chemist, I would take the following approach.

Providing something harmala-like crystallizes from the salt saturated solution, I would then unsaturate the solution by adding lots of water. Then I would make the solution basic to see if any of the metal compounds crashes out. If they do, then I guess the separation worked, if they dont, then I guess it didn't.

This sound reasonable?

 

[The Day Tripper]

So lets say one separated the harmine/harmaline from their rue extract, took the harmaline, dissolved it in hcl water, then added zinc dust and stirred/let sit for at least half a day, then filtered out any remaining zinc. then freebased it with naoh at ph 10, finally filtering, collecting, and drying the precipitates.

And assuming the thh fb is fairly soluble in dry alcohols, and zinc carbonate is not, could you take the fb thh, dissolve it in an minimal amount of warm alcohol (dry iso), filter out the zinc, then add a few drops of %30 hcl? Or perhaps a fasa/tartaric acid saturated dry alcohol?

Would you precipitate only thh hcl's/tartarates/fumarates, as they would be insoluble in the dry(ish few drops of water from the hcl) alcohol? The zinc would not be there, so thats not going to be a problem, and worse comes to worse just evaporate it if nothing precipitates. If your using hcl, you could even add a np (heptane/limo) to force precipitation if the hcl's are soluble to an extent in the alcohol.

The only worry i have about fb harmalas in alcohols is the red reaction. If you can get it dissolved and precipitated, filtered, dried as quickly as possible, perhaps it will prevent the red (harmala oxides i think) from forming. Assuming thats even a problem with thh.

Sound like a reasonable plan? I have a few grams of rue extract I'd love to try this on.

Also, i have a few gram buffalo 99% zinc bars. Would this be a viable source of zinc? or is powder the only option?

I know its not going to have the reactive surface area as powder, but from what i understand the zinc dissolves, so it might just take longer to dissolve/react. I'll be buying some elemental zinc powder anyway, but it would be cool if i could try this soon with what i already have.

And finally, how many grams of zinc should be added relative to the fb harmaline? Should i just add enough hcl to dissolve the harmaline or is excess needed for the reduction?

And help here is appreciated-

thanks-

 

[The Day Tripper]

Zinc chloride is uber soluble in water, and formed by reacting zinc and hcl-

Zinc chloride - Wikipedia

en.wikipedia.org

Now does it precipitate when based? If so, would there be a window of opportunity where the ph was high enough to precipitate the thh, but not the zinc? Or v/v and precipitate/filter the zinc first?

 

[evil804]

would i be able to make my own zinc suitable for this reaction by taking a common zinc supplement (i have zinc gluconate on hand. 25mg before bed leads to vivid lucid dreams!) and adding base to give me a freebase zinc? i have a bunch of seperated rue harmalas as i prefer harmine, and i would love to convert my harmaline to THH for an extra oomph to my usual dose of harmine!

 

[Luuk]

Has there been any progress with this? I'm really looking forward to trying this. I've got a mountain of rue harmalas, zinc dust, and access to most common solvents and acids/bases. I don't really care about using weak acids/bases.
The conversion in literature happens with ammonium chloride and ammonia, but yield was lower there, right? Would this be because of HCl used, or because of ammonium chloride and ammonia?

Possible procedure no1:
Acidify harmaline with household vinegar (pure acetic acid) and add zinc, then basify with ammonia in presence of ammonium chloride to prevent zinc salts from forming. Precipitate should be pure THH freebase. Maybe lower yield like in literature if lower yield was because of ammonium chloride and ammonia used, and not because of HCl?

Possible procedure no2:
Acidify harmaline with household vinegar (pure acetic acid) and add zinc, then basify with high concentration NaOH solution. This way the zinc hydroxide precipitate should dissolve and leave only THH freebase. But are there really no other zinc salts present?

Could someone with the know-how please elaborate on these procedures? Am I correct?

Let's develop a final tek to make THH available for everyone!

 

[Cosmic_Revolution]

I came across this link from the Shroomery actually!! But Im still not 100% on what form of Zinc you all are talking about. Is it just pure Zinc, I'm no chemist and I'm used to people referring to different forms of molecules. Like Freebase DMT or DMT Fumarate. I would love it if some one could tell me exactly what I need and maybe provide a link to the exact product. The reason Im posting this is because I just got done looking online for pure Zinc and all I'm finding is Zinc Acetate, Zinc Oxide etc... Please and thanks guys I don't want to buy the wrong thing.

 

[Mitakuye Oyasin]

So, which Nexian is going to make inexpensive THH available to all of us and compete with FV?

 

[joedirt]

What is it about a molecule that makes it precipitate in a NaCl saturated solution but others not?

electrostatic vs. van der waals interactions.
this is the basis behind ion exchange chromatography, where bound analytes are displaced from the charged functional groups of ion-exchange resin by changing either the pH or salt concentration, or both. and yes, DMT can be precipitated with a high enough salt concentration, assuming it's in free base form where the net charge is zero, because the overall molecule has predominantly van der waals interactions (it's mostly hydrophobic)

It has a lot more to do with the entropy of the floppy side chain containing the primary amine in DMT vs the relatively restricted amine in harmalas.

Because harmalas show a lot less relative atomic movement at the positive nitrogen they can association with an free salt ion in a much easier fashion and with higher affinity.

I base this on work free energy calculations I did around primary amines ( within macrocycle side chains) a few years back.

Edit: Actually after rereading what you wrote I do agree, but I still stand by the much larger entropy from sidechain rotation as the predominant difference between DMT precipitates and Haramalsas.

BTW I'd bet DMT freebase could be io exchanged as well. May have to drop the temperature a bit to get it to crash out of solution, but I bet it would be possible.



Peace.

 

[endlessness]

Has anyone tried doing the manske with this yet to remove the metallic compounds?

If not, i may try it myself. As I'm no chemist, I would take the following approach.

Providing something harmala-like crystallizes from the salt saturated solution, I would then unsaturate the solution by adding lots of water. Then I would make the solution basic to see if any of the metal compounds crashes out. If they do, then I guess the separation worked, if they dont, then I guess it didn't.

This sound reasonable?

So your plan is to precipitate the freebases + zinc, redissolve in acidic solution, precipitate by salt-saturating and then after retrieving alkaloids, basing to see if zinc precipitates out? Sounds reasonable to me, but im not sure how one could be 100% sure it would have worked.

Be sure to post back results before consuming, so we can all think about it collectively.

Im gonna research about assays for metalic compound, if there's any reagent that could tell if there's zinc in the mixture. Any of the chemists or experts (benz, inf, joedirt, etc ) got any idea?

So lets say one separated the harmine/harmaline from their rue extract, took the harmaline, dissolved it in hcl water, then added zinc dust and stirred/let sit for at least half a day, then filtered out any remaining zinc. then freebased it with naoh at ph 10, finally filtering, collecting, and drying the precipitates.

And assuming the thh fb is fairly soluble in dry alcohols, and zinc carbonate is not, could you take the fb thh, dissolve it in an minimal amount of warm alcohol (dry iso), filter out the zinc, then add a few drops of %30 hcl? Or perhaps a fasa/tartaric acid saturated dry alcohol?

Would you precipitate only thh hcl's/tartarates/fumarates, as they would be insoluble in the dry(ish few drops of water from the hcl) alcohol? The zinc would not be there, so thats not going to be a problem, and worse comes to worse just evaporate it if nothing precipitates. If your using hcl, you could even add a np (heptane/limo) to force precipitation if the hcl's are soluble to an extent in the alcohol.

The only worry i have about fb harmalas in alcohols is the red reaction. If you can get it dissolved and precipitated, filtered, dried as quickly as possible, perhaps it will prevent the red (harmala oxides i think) from forming. Assuming thats even a problem with thh.

Sound like a reasonable plan? I have a few grams of rue extract I'd love to try this on.

Also, i have a few gram buffalo 99% zinc bars. Would this be a viable source of zinc? or is powder the only option?

I know its not going to have the reactive surface area as powder, but from what i understand the zinc dissolves, so it might just take longer to dissolve/react. I'll be buying some elemental zinc powder anyway, but it would be cool if i could try this soon with what i already have.

And finally, how many grams of zinc should be added relative to the fb harmaline? Should i just add enough hcl to dissolve the harmaline or is excess needed for the reduction?

And help here is appreciated-

thanks-

Many questions there that I can't really answer due to lack of tests/knowledge, but your alcohol plan might work. Try it out, maybe side by side with manske precipitation as the poster quoted above, and we can compare the results. Again, do let us know results so we can think about it before consuming. Lets work on this together!

Regarding zinc, dont know what that bar you mentioned is, if its zinc oxide or some other form of zinc, it wont work, it has to be pure elemental zinc. Also not sure if it works if its not powdered. As for amounts, just add excess of it I guess, not sure on the numbers. As for HCl, you can add enough to dissolve plus a bit more to make sure its enough H+ around for the reduction.

Zinc chloride is uber soluble in water, and formed by reacting zinc and hcl-

Zinc chloride - Wikipedia

en.wikipedia.org

Now does it precipitate when based? If so, would there be a window of opportunity where the ph was high enough to precipitate the thh, but not the zinc? Or v/v and precipitate/filter the zinc first?

I think when you base a solution containing Zinc chloride, it wont be in chloride form anymore, but will form zinc carbonate or zinc hydroxide or whatever base you use.

would i be able to make my own zinc suitable for this reaction by taking a common zinc supplement (i have zinc gluconate on hand. 25mg before bed leads to vivid lucid dreams!) and adding base to give me a freebase zinc? i have a bunch of seperated rue harmalas as i prefer harmine, and i would love to convert my harmaline to THH for an extra oomph to my usual dose of harmine!

Nope you need pure zinc.

Has there been any progress with this? I'm really looking forward to trying this. I've got a mountain of rue harmalas, zinc dust, and access to most common solvents and acids/bases. I don't really care about using weak acids/bases.
The conversion in literature happens with ammonium chloride and ammonia, but yield was lower there, right? Would this be because of HCl used, or because of ammonium chloride and ammonia?

Possible procedure no1:
Acidify harmaline with household vinegar (pure acetic acid) and add zinc, then basify with ammonia in presence of ammonium chloride to prevent zinc salts from forming. Precipitate should be pure THH freebase. Maybe lower yield like in literature if lower yield was because of ammonium chloride and ammonia used, and not because of HCl?

Possible procedure no2:
Acidify harmaline with household vinegar (pure acetic acid) and add zinc, then basify with high concentration NaOH solution. This way the zinc hydroxide precipitate should dissolve and leave only THH freebase. But are there really no other zinc salts present?

Could someone with the know-how please elaborate on these procedures? Am I correct?

Let's develop a final tek to make THH available for everyone!

Proceedure one seems good since its what is described in literature at times. Proceedure 2 I dont think so, since zinc hydroxide will also precipitate I think, or am i missing something?

I came across this link from the Shroomery actually!! But Im still not 100% on what form of Zinc you all are talking about. Is it just pure Zinc, I'm no chemist and I'm used to people referring to different forms of molecules. Like Freebase DMT or DMT Fumarate. I would love it if some one could tell me exactly what I need and maybe provide a link to the exact product. The reason Im posting this is because I just got done looking online for pure Zinc and all I'm finding is Zinc Acetate, Zinc Oxide etc... Please and thanks guys I don't want to buy the wrong thing.

It has to be pure zinc, not acetate, oxide etc. The ebay link you sent me by pm should work

What is it about a molecule that makes it precipitate in a NaCl saturated solution but others not?

electrostatic vs. van der waals interactions.
this is the basis behind ion exchange chromatography, where bound analytes are displaced from the charged functional groups of ion-exchange resin by changing either the pH or salt concentration, or both. and yes, DMT can be precipitated with a high enough salt concentration, assuming it's in free base form where the net charge is zero, because the overall molecule has predominantly van der waals interactions (it's mostly hydrophobic)

It has a lot more to do with the entropy of the floppy side chain containing the primary amine in DMT vs the relatively restricted amine in harmalas.

Because harmalas show a lot less relative atomic movement at the positive nitrogen they can association with an free salt ion in a much easier fashion and with higher affinity.

I base this on work free energy calculations I did around primary amines ( within macrocycle side chains) a few years back.

Edit: Actually after rereading what you wrote I do agree, but I still stand by the much larger entropy from sidechain rotation as the predominant difference between DMT precipitates and Haramalsas.

BTW I'd bet DMT freebase could be io exchanged as well. May have to drop the temperature a bit to get it to crash out of solution, but I bet it would be possible.



Peace.

But how, in your reasoning, does this explain why vasicine/vasicinone/deoxyvasicine dont precipitate ?

 

[joedirt]

But how, in your reasoning, does this explain why vasicine/vasicinone/deoxyvasicine dont precipitate ?

Deoxyvasicine would almost certainly crash out of solution as well, but the tertiery amine is not nearly as basic as the primary amine in DMT so it is possible that DMT would snatch the salt ion before deoxyvasicine...but I doubt it. Deoxyvasicine looks pretty hydrophobic to me.

Vascine and vascicone however, actually look to be very water soluble to me. The vasicine hydroxyl group would form an H-bond to the Oxygen in water and one of the water molecule hydrogens would hydrogen bond to the sp2 nitrogen of vascine and vascicone. This would actually be quite stable when you factor in very little rotation entropy is introduced from floppy side chains like you see in DMT. Also the primary amine on DMT is more basic than the tertiary amine on vasciscine and vascicone thus making it more readily available to form an ionic salt bond.

BTW I'm just speculating with benzyme that it could be done. I don't know for sure. If I was going to do it I would use three times the volume of water with saturated salt. Saturated via heating and stirring with some left sitting on the bottom. I'd then pour that into a hot water/Freebase DMT solution. Then I'd cool it very slowly for 24 hours and if no precipitate then I'd stick it in the fridge for a up to a week. I'm guessing it would precipitate out with 24 hours of being put in the fridge...but that is just a guess.


Peace

 

[endlessness]

I think I might have found an easy way to separate THH from zinc.

When sodium hydroxide is added a solution of THH+zinc (from harmaline reduction), both THH as well as zinc hydroxide precipitate. But when excess sodium hydroxide is added, zinc hydroxide becomes sodium zincate, which will be soluble in the solution while THH should remain insoluble. Then one can just filter and have THH without zinc.

( Zn(OH)2 (s) + 2 OH- (aq) ---> [Zn(OH)4]2- (aq) )

Im gonna test that in the future.

Im also currently trying to do the reduction on a mixture of harmine and harmaline, see if zinc is strong enough to reduce both. Im gonna try manske too, see if it can separate THH from zinc.



Btw joedirt, im pretty sure deoxyvasicine does not crash out of solution, at least it did not show up in any analysis done by post-manske precipitates (maybe it just wasnt there in the first place? Gotta check again the results). Also I dont understand where you got the 'precipitating dmt with manske' idea, I thought we were just discussing harmalas here. Anyways thanks for the info