DMT-Oxide to DMT using zinc - required conditions

[Hailstorm]

Most teks to convert DMT-Oxide to DMT suggest using powdered zinc.

But what conditions are required for that reaction to occur?

1) DMT-Oxide salts in acidic water: for example, in the context of a drytek A/B DMT extraction, will the DMT Oxide to DMT conversion work if powdered zinc is added to the acidified plant material?

2) DMT-Oxide freebase in basic water: will it work if the zinc is added to the mud pie *after* the basification with calcium hydroxide?

3) DMT-Oxide freebase in a non-polar aliphatic hydrocarbon solvent: will it work if powdered zinc is added to the heptane solution prior to DMT recrystallization?

4) DMT-Oxide freebase in acetone/IPA: will it work if powdered zinc is added to acetone or IPA after dissolving the freebase and prior to adding FASA/FASI?

5) DMT-Oxide fumarate in water: will it work if one dissolves the fumarates in water that has powdered zinc mixed in?

6) DMT-Oxide fumarate in acetone/IPA: will it work if one washes the fumarates in cold acetone or IPA with powdered zinc mixed it?

Finally, does the temperature matter?

 

[downwardsfromzero]

Option 5 only. All other options will either not work or lead to some form or other of mess.

Stirring is important and you'll probably find better results if atmospheric oxygen is excluded somehow.

What makes you sure that you're reducing DMT oxide anyhow? The orange colour comes from something else.

 

[Hailstorm]

So 5) zinc can de-oxidize DMT already bonded with fumarate ions? Would you recommend water+zinc wash after FASA/FASI extraction then?

(I wonder if the fumarate monoanion interacts with both nitrogen atoms in DMT via the same hydrogen bonds as what happens with 4-Aco-DMT fumarate: The Crystal Structure of 4-AcO-DMT Fumarate?)

---

...Regarding DMT oxide being a yellow wax - it seems to be the consensus? Here are a few posts implying the yellow color of the DMT oxide:
DMT(s) Analysis Compilation [1H-/13C-NMR/HPLC/LC-MS] - Plant Analysis and Substance Testing - Welcome to the DMT-Nexus
Yellow/brown gunk=DMT oxide? - Advanced/Enhanced chemistry - Welcome to the DMT-Nexus
Mini A/B still yielding yellow result. - A/B - Welcome to the DMT-Nexus
DMT N-Oxide to Freebase DMT - Advanced/Enhanced chemistry - Welcome to the DMT-Nexus.

(interestingly enough, benzyme is suggesting that it is the indole nitrogen atom that gets oxidized before the amine one - in that case, are there 2 different types of DMT oxides - DMT monooxide and DMT dioxide, with 1 and 2 nitrogen atoms oxidized, respectively?)

 

[downwardsfromzero]

Glad to see you've been doing your background reading. Could you be a darling, please, and edit your post so that the links are active (hxxps -> https)? [Done, thanks!]

In solution, DMT fumarate occurs as positively charged, protonated DMT cations, and negatively charged fumarate anions. The DMT and fumarate ions are not bonded together when in solution.

DMT-N'-oxide tends to occur in leaves. Maybe you are working with leaf extracts? Or did you produce the oxide by treating DMT with hydrogen peroxide?

To suggest that the yellow wax is DMT-N'-oxide without conclusive chemical analysis is merely an assumption. We'll have to admit that this assumption has been propagated for quite some time. As I perceive it, Benzyme suggests that an oxidation occurs at the pyrrole ring of the indole portion of the molecule. Oxidation can also mean loss of hydrogen, or loss of one or more electrons. Addition of an oxygen atom to the molecule is only one of the possible interpretation of the phrase, "oxidation occurring at the pyrrole ring". Joining two DMT molecules together at the 2- position would certainly produce a coloured molecule and this would be an oxidation. Look at the formation of indigotin from indoxyl.

In any case, an unsubstituted pyrrole nitrogen does not particularly lend itself to N-oxide formation.

 

[Hailstorm]

No leaves, no peroxide - an MHRB extract (vinegar, Ca(OH)2, Naphtha, freeze-precipitation, fan drying, no re-X) stored for more than a year in a dark airtight place, but under moderate ambient temperature (no freezing).

Unless my memory is betraying me, it used to look pure white. Now it looks slightly off-white (pale yellow - very similar to this picture). Dissolving in hot heptane resulted in a thin viscous yellow layer at the bottom - again, very similar to this recent thread.

Whether it is some kind of plant oil, DMT-N-oxide, or another alkaloid, I don't know. I plan to experiment with zinc to see how much difference it makes. The idea is to make DMT fumarate out of the off-yellow freebase, dissolve it in water, heat the water up, treat half of it with zinc, freebase both halves, pull with heptane, and see if there is any visual difference.

 

[endlessness]

If you're doing this for scientific experimentation purposes, be sure to not just compare before vs after but to have a control group, for example a part of your product where you also redissolve in water and recrystallize doing everything the same except not adding zinc.

If you want to further experiment, you could also get some DMT and use hydrogen peroxide to purposely oxidize it and then do the conversion

It would be also interesting if you use some sort of analytical method, like TLC.

IME the change in color is insignificant in terms of molecular change and wont even show up with LC-MS. I think Benz also said the same. Maybe has to do with polymorphism of DMT, maybe it's only trace amount of oxidation that affects macroscopic color in a way that misleads us to think its a lot, or whatever.... Either way, let us know if you do experiment.

Be well

 

[benzyme]

I'm not sure where I've read it, but oxidation (loss of electrons, which have negligible mass, and thus, won't show up in the spectra) occurs in the pyrrole moiety; this is what gives dmt, and other tryptamines, its yellow/orange color. The n-oxide, when actually present, will show up as a smaller secondary peak at 205 m/z (base peak being 189 m/z, DMT). For dmt to get to n-oxide, it's typically from pyrolysis (or similar harsh conditions), or treatment with an oxidizer like conc. H2O2.

if the color of old dmt bugs ya, you could do another A/B on it, or convert it to an antioxidative salt, like fumarate.

an experiment I may conduct is adding some dmt to HCl, and some other dmt to hcl with a scored penny; I'd think the color change back would be caused by H+ (acid) anyway.

 

[Hailstorm]

To practice on small amounts, a mini-experiment was conducted on three 200mg samples of DMT freebase freshly extracted from MHRB via A/B (acetic acid, calcium hydroxide) followed by a single pull with heptanes and freeze precipitation.

Each sample looked off-white (beige) - image 1. Each was put into its own vial.

Sample A was kept in a freezer in an airtight container, then liquified for visual comparison with the other samples. Sample B spent 24 hours on a 60°C hotplate under a fan blowing outside air downwards (no direct sunlight). Sample C was placed next to Sample B (identical conditions) but also treated with excess (2-3ml) 3% hydrogen peroxide.

The expectation was that sample A would not degrade, sample B might change, and sample C would turn into DMT oxide.

You can see the results on images 2 and 3 (close-up). Sample B looked a bit more yellow than sample A, but it may not be a sign of a chemical reaction - sample B could simply be drier, denser and therefore more opaque. The peroxide, as you can see, obliterated sample C, turning it into dry, brown, bubbly wax. It is unclear if that was DMT oxide alone or with some other decomposition products.

To each sample approximately 10ml of heptanes was added (image 4) and heated up to near the boiling point; all 3 samples were placed on the hotplate and the evaporation process was closely monitored.

Sample C remained mostly insoluble. In fact, it remained very dense and hard to scrape off the walls. It emitted overwhelming odor of burned DMT (that horrific "bad breath" smell) despite the fact the the temperature of the hotplate did not exceed 115°C.

Samples A and B remained transparent, tinted slightly yellow. Each continued to smell like extracted DMT freebase.

Samples A and C were removed from the hotplate. Close attention was paid to sample B to see if there were any signs of degradation/decomposition (such as the yellow/orange oil at the bottom that used to appear in re-X of old Naphtha extracts). No such signs were detected - sample B remained completely clear before starting to precipitate out (image 5).

The outcome is: if the substance in sample C was indeed DMT oxide, then it was not detected in sample B after 24 hours of heat and outside air exposure. There is no apparent reason to treat sample B with zinc. Sample C could probably be treated with zinc, but I am now questioning the very idea of converting DMT oxide back to DMT if thermal or chemical burning is the only realistic way to obtain it.

However, I find it hard to dismiss the broad consensus (and multiple reports) that the freebase degrades unless stored in a cold, dark, oxygen-free environment. I need to find a way to "age" DMT naturally, since 1 day of oxygen exposure is clearly not enough.

 

[Jees]

^^ Upvoted for efforts :thumb_up:

 

[sbios]

Very interesting. Thanks for sharing the experiment.

No leaves, no peroxide - an MHRB extract (vinegar, Ca(OH)2, Naphtha, freeze-precipitation, fan drying, no re-X) stored for more than a year in a dark airtight place, but under moderate ambient temperature (no freezing).

I'm curious why you used a new batch instead of the one year old (possibly oxidized) batch/ maybe you don't have no more?

Seems to me a related question to experiment on is: convert DMT freebase -> DMT fumarate (which I think already have some references somewhere) since dmt fumarate can be store longer without oxidization (not sure if I remember this correctly). So that'd solve your long term storage issue. Then when you need, convert dmt fumarate back to freebase.

 

[Hailstorm]

I'm curious why you used a new batch instead of the one year old (possibly oxidized) batch/ maybe you don't have no more?

The new batch was extracted with an unspecified mix of n-Heptane isomers. While it is not reagent grade, as a solvent it should be close enough to pure n-Heptane (which I plan to get one day). Heptane is very selective to non-polar compounds like DMT so hopefully it should not have pulled many plant oils or other impurities. The only source of yellow/orange goo at the bottom would have been degradation products (or so I hoped).

The old DMT was extracted with Naphtha. Since it contains pentane (and god knows what else) it is less selective so it may have pulled some junk in, and it would have been unclear if DMT oxide was part of that or not.

Seems to me a related question to experiment on is: convert DMT freebase -> DMT fumarate (which I think already have some references somewhere) since dmt fumarate can be store longer without oxidization (not sure if I remember this correctly). So that'd solve your long term storage issue. Then when you need, convert dmt fumarate back to freebase.

This is indeed the consensus. However, nothing organic lasts forever, and it will be interesting to test the limits of DMT fumarate too.

 

[downwardsfromzero]

Congrats on promotion, your efforts have not gone unnoticed!

The peroxide treated sample 'C' has almost certainly become more polar - have you tested its solubility in solvents more polar than alkanes? Its lack of solubility may also stem from polymerisation (this is just guesswork, however) but reduction might sort that out. I would love to see how that oxidised sample responds to zinc reduction, and whether it's possible to recover DMT from it.

nothing organic lasts forever, and it will be interesting to test the limits of DMT fumarate too.

Store some under pressure in pure oxygen?

 

[Hailstorm]

Congrats on promotion, your efforts have not gone unnoticed!

Thanks!

The peroxide treated sample 'C' has almost certainly become more polar - have you tested its solubility in solvents more polar than alkanes?

Sadly, I did not think of it. It did dissolve it in the very diluted (0.1M) HCl and easily formed a clear amber liquid.

Its lack of solubility may also stem from polymerisation (this is just guesswork, however) but reduction might sort that out.

I wonder if evaporating diluted H2O2 is the "proper" way to make DMT oxide. During that process the concentration increases, and eventually DMT gets into contact with concentrated H2O2. The solution, having remained yellow for most of the process, rapidly darkens into amber, then "DMT cola"; at the very end there is intense formation of small bubbles (O2? or even CO2 - hence the burned DMT smell?) before the semi-solid mass traps the last bubbles inside.

I would love to see how that oxidised sample responds to zinc reduction, and whether it's possible to recover DMT from it.

I think it makes sense to try anew - with more material and yield calculation (assuming it works at all). It will take a few days to obtain more concentrated reagents, since Zn does not seem to react with 0.1M HCl at all.

Just to double check on the plan:

1) DMT + H2O2 => DMT-O + H2O
2) Zn + 4HCl + 2DMT-O => ZnCl2 + 2DMTCl + 2H2O
3) A/B with HCl and NaOH, a few pulls, evaporation and weighing?

 

[downwardsfromzero]

Great to hear that you're carrying on with the experiments!

It does sound like the DMT over-oxidised as the peroxide evaporated. The bad smell is likely to be due at least in part to indole produced when the side-chain gets lopped off. Perhaps a more dilute solution of peroxide in an amount corresponding to the molar quantity of DMT would do the job a bit more gently? And dissolve the DMT in ethanol first?

Your outline scheme is OK-ish, although the equation for part 2 will look more like: Zn + 3HCl + DMT-O => ZnCl2 + DMT.HCl + H2O.
In part 3, you've already added acid in part 2. You might want to avoid a precipitate of zinc hydroxide by spiking the solution with ammonium chloride and using ammonia as the base instead of NaOH. Zn(OH)2 can dissolve in an excess of NaOH, but this doesn't necessarily mean that it will. Fine particulates of Zn(OH)2 might lead to an emulsion problem.

 

[Hailstorm]

I wanted to provide a quick update.

The experiment (freebase -> oxide -> freebase) did not work well - the yield was abysmal, 10% (40mg from 376mg) due to the following 7 mistakes made.

1. The first mistake may have been evaporating the unreacted peroxide and IPA. Near the end the peroxide concentration increase seemed to outpace the speed of evaporation, yet all the alcohol had already evaporated and could no longer protect the freebase from over-oxidation / polymerization. This time there was no strong smell of burned DMT, but the brown color was back again, and so were the large bubbles.

At the same time, it is possible that DMT was not burned - perhaps DMT-N-Oxide simply has that dark amber color, and the bubbles were large because the liquid became very viscous?

2. The second mistake may have been adding HCl before giving the residual DMT-Oxide oil enough time to completely dry up. If there were trace amounts of peroxide left in the solution, HCl would have reacted with H2O2 to form chlorine gas and HOCl - not good (chlorine is poisonous, HOCl reacts with NaOH to produce bleach).

3. The third mistake was eyeballing zinc and using too much. The suspension had to be filtered twice, possibly with some loss of DMT in the process.

4. The fourth mistake was stopping the HCl + Zn reaction after 2-3 hours. The intensive bubble formation had ceased but the reaction was probably still going on, albeit at a reduced rate. Perhaps letting diluted HCl evaporate a bit and then adding fresh acid, etc. would have kept the reaction going, and led to more DMT-Oxide getting converted to freebase.

5. The fifth mistake was not using enough NaOH to dissolve zinc hydroxide (the suggested ammonium hydroxide also causes the formation of Zn(OH)2 so it does not seem any better?). A bunch of zincates formed and did not dissolve. This was not a big hassle since the unreacted zinc dust had to be filtered off anyway, but the zincates tend to clog the filter paper, and the wet mess traps some liquid.

6. The sixth mistake was clumsy (and rushed) liquid-liquid extraction with hot heptane. One pull bumped upon opening the stopper (as the heptane boiling point dropped with the reduced pressure) leading to some DMT loss (thankfully, no injuries). Heptane is the least polar solvent so it should be great for pulling just the freebase w/o the oxide, but it requires multiple pulls, needs to remain hot, so it takes quite some skill and patience.

7. The seventh mistake was freeze precipitation and scraping. While it is great for extractions, scraping all the crystals off the evaporation dish is impossible so it leads to some DMT loss.

...

I believe the experiment should be re-done. I have a few ideas of how to perform it using no heat, no evaporation, and no filtration - trying to keep it as kitchen-friendly as possible.

This time, I am considering the following plan:

1. Convert DMT freebase to DMT Oxide.

Dissolve 376mg freebase in a vial with 5ml of 5% vinegar and add 15ml of 30% hydrogen peroxide. The acetic acid is used instead of alcohol to avoid having to evaporate it.

I assume that without evaporation DMT dissolved in alcohol will be impossible to pull with a non-polar solvent later

I have no idea how fast this reaction is. Perhaps it happens instantly, but waiting a day or two should not hurt.

2. Make ALL the hydrogen peroxide decompose.

Add a tiny (catalytic) amount of manganese(iv) oxide to the vial and observe O2 bubbles. Once they stop, repeat until adding more catalyst no longer makes any difference.

Test if all the H2O2 is gone by taking a sample and dropping it into an indicator solution - like KMnO4 dissolved in a strong acid.

Can (and should) KMnO4 be added to the DMT solution directly - can it perhaps replace MnO2 altogether as both an oxidizing agent and self-indicator? Will it react with DMT? Will it be too slow to change its color in the weak (acetic) acid environment?

Another option for the catalyst is potassium iodide. The benefit is that KI is soluble in water. I assume that in acidic conditions it will precipitate out as iodine, however.

3. Add Zn and HCl to convert the DMT Oxide to DMT (chloride).

Pour the test vial into a 250 ml flask. Add 35ml of 2M HCl and begin stirring continuously on a magnetic stirrer.

If MnO2 was used in the previous step and not filtered off, HCl will produce chlorine (gas). HCl would not react with KI.

Slowly add zinc mesh until the zinc is no longer reacting/disappearing. Once it stops reacting, and add a touch of fresh HCl to make zinc disappear so that there is no zinc dust to filter off. After that procedure the solution should be slightly acidic and mainly contain H+, Zn++, DMT+, Cl-, CH3COOH- ions, and OH- groups.

4. Basify the solution to convert the DMT chloride to DMT freebase.

Keep adding NaOH until all the Zn(OH)2 turns into Zn(OH)4, which dissolves completely. Again the solution should be mostly clear, with pH above 13.

MnCl2 will produce Mn(OH)2, which will not dissolve. Again, KI wins by not reacting with NaOH, it seems..

5. Extract the DMT freebase with a highly non-polar solvent.

Do multiple pulls with hot heptane (unless there are better alternatives?), evaporate the heptane down to an amount that can be poured into a small dish that is light enough for weighing on a milligram scale. Weigh the dish while empty and again after all the heptane evaporates, subtract the weights to calculate the yield.

6. Bioassay the product to make sure it is DMT freebase and not something else.

 

[Hailstorm]

The second experiment failed completely. I am still going to describe it, but one of the steps below leads to a complete loss of DMT - I just do not know which one.

1) Step 1 - converting DMT to DMT-Oxide using hydrogen peroxide

In vial "D", 0.02 moles (376mg) of pure DMT were dissolved in 5ml of distilled 5% vinegar. 15ml of 30% hydrogen peroxide was added.

Vial "M" contained just 5ml of vinegar and 15ml of peroxide.
Vial "T" contained only 5ml of vinegar and 15ml of distilled water.

All 3 vials were covered (not airtight) and left alone for 5 days at room temperature. During that period, the liquid in vial "D" slowly darkened.

 

[Hailstorm]

2) Step 2 - making the peroxide decompose

To all 3 vials 4ml of 2M NaOH (320mg) was added to basify each solution (a bit of precipitate was observed in vial "D" ). This basification was required for iodine ions (see below) to act as a catalyst, which requires non-acidic conditions.

Then to vials "D" and "M" catalytic amounts (15-20mg) of potassium iodide were added to speed up the decomposition of hydrogen peroxide.

Intense O2 bubbling began and only stopped after 3 days. The vial "M" in the middle is showing the residual iodine coloration that did not disappear.

 

[Hailstorm]

3) Step 3 - reduction with hydrochloric acid and zinc

The liquid from vial "D" was transferred to a 250ml Erlenmeyer flask.

~50ml of 2M hydrochloric acid was added. No bubbling was observed, indicating that the hydrogen peroxide may have indeed decomposed completely. A quick pH test confirmed that the solution was strongly acidic (pH around 1).

The acidic solution was continouosly stirred on a magnetic stirrer.

3g of zinc was added gradually. Each portion was allowed to dissolve before the next one was added. Over time, zinc began to dissolve more and more slowly, as expected. At the end, most of the acid was neutralized (pH around 6) and the solution was opaque. A few pellets of zinc were allowed to remain in the flask.

 

[Hailstorm]

4) Step 4 - basification with sodium hydroxide

Adding distilled water and sodium hydroxide while stirring produced a lot of white precipitate. It would not dissolve, making the solution look thick and creamy.

More water, and a lot more sodium hydroxide was added. Eventually (beyond pH ~ 13) the precipitate (zinc hydroxide) dissolved (into zincate ions) and the entire solution cleared up.

Apart from a few surviving pellets of zinc, there was no precipitate that would resemble, for example, DMT freebase.

 

[benzyme]

reduction is a hydrogenation reaction... that's not going to happen in alkaline conditions.