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URBAN MYTH: yellow polymorph Options
 
AbsolutelyPureDMT
#1 Posted : 6/21/2023 5:05:45 AM

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This is a hopefully valuable archive of a Reddit reply I made containing intricate details of DMT crystallography and spectroscopy. It is addressed to Reddit moderator ClobWobbler who claims reliance on Benzyme posts. I hope a mod can place it for a wider audience here, thanks, as I’m still a junior member. Next post will be about FASA method being obsolete folly.

ClobWobbler, misguided by Benzyme: this is a difficult post to write so sorry to be so blunt. You’ve been simply wrong about a yellow polymorph dimer that can depolymerize during smoking for years now due to lack of advanced training in organic and physical chemistry.

I have deduced the exact structure of the colored dimer involved and it’s far too covalently tough to split back into monomer DMT under mild heat of vaporization because it’s not only coupled in two but then it naturally oxidizes to create a more stable fully conjugated dimer that is highly colored but amorphous at room temperature so quite sticky. It’s also not very soluble so it oils out with or before DMT.

Besides a covalently linked “dimer” there’s no other type of dimer appropriate to claim for DMT, and has never been mentioned in the alkaloid literature nor the entire corpus of organic chemistry. Hydrogen bonding is awkward for DMT as the only donor is the bulky flat indole ring and the only acceptor has bulky methyl groups so a dimer would rip apart by entropy under Brownian motion, not exist as a lingering 14 membered ring of DMT backbones via a mere two hydrogen bonds. Charge transfer doesn’t exist with a sole boring alkyl indole. DNA is a hydrogen bonded dimer, designed for donor/acceptors to perfectly line up.

Trace amounts of dimer that still afford 99.99% pure DMT can readily taint full DMT crystals, but never does the yellow go away upon melting or dissolution of the crystals. The only “yellow polymorph” mentioned in the classic paper on colored DMT was indeed cited as amorphous. They only characterized three colorless polymorphs, discarding the waxy solidified yellow mass.

The molecular orbital energy levels involved in DMT itself make it impossible that mere crystal packing forces can shift the mere two ring indole group all the way from the deep UV region of absorption over to the visible region. A mere two neutral aromatic rings show a spectrum peak nowhere near the visible region. So just like highly sensitive drug tests can detect nanograms by forming strong visible dyes, yellow DMT is from an impurity that can’t be removed easily since even fractions of 1% of it colors crystals like food coloring colors sugar crystals on a stick:


Laboratory students out there who test yellowed DMT simply cannot find the impurity since it’s still at only trace levels and their samples are not analytical standards to begin with so 0.1% impurity that happens to be a strong dye goes undetected. Yet they still get odd little baseline peaks. That’s the yellow, you just don’t have a reference to assign them exactly, yet. But they integrate to only trace mass? Yup.

The extended pi-system of carbazoles like harmine allows them to just barely exit the UV band and enter the visible (blue) band which lets them reflect yellow to us. The DMT dimer that oxidatively couples then as is typical reforms a double bonded system by oxidizing again to loose H2 is an even bigger chromophore.

Philosophically you have been correct that yellow color doesn’t really matter for DMT purity because that yellow represents a very strong dye you can see at even trace levels. The giveaway is how the exact same yellow taint fully remains upon crystal melting. Polymorphism effects should disappear where crystals are melted down, but the color remains!

You also now have my report of ridding yellow via purification. Tough, drawn out, multi-stage, multi-strategy purification. I made the FASA method obsolete in the process, learning that hot DMSO and acetone could recrystallize the fumarate at very compact volume what acetone alone required gallons. It was the fumarate steps that let me achieve real progress in ridding straw color traces.

Here is the actual very likely dimer structure based on the known reactivity of indole derivatives similar to DMT:


2,2-bisindole itself is a brown solid, consistent with being a very strong light absorber that if diluted would show as orange or eventually yellow.


Or there just might be a CH methylene group coupling them at the same points if the first step is reversible reaction with carbon dioxide in the air, prior to dehydration to a double bond ethylene group then coupling to a second DMT. Tryptamines in general do this with aldehyde impurities and the paper on yellow DMT only got their yellow sample from acetonitrile which is notoriously hard to purify of acetaldehyde content.

And here is the UV/VIS spectra of DMT and harmalas showing how the yellow harmalas just barely reach a peak edge into the visible region (400-700nm) whereas DMT has a huge electronic gap from interacting with visible light:


Mere crystal packing forces on such a boringly neutral molecule cannot shift the fundamental absorption energies of the isolated indole ring. Color polymorphism comes from long extended dye molecules being readily twisted due to crystal packing forces. DMT isn’t a chromophore at all.

The DMT dimer however is another significant step larger in unconjugated size so becomes a much stronger dye than the harmalines. But DMT itself is just an indole lacking but a boring alkyl side chain and so is just too small in size with a way too large band gap between LUMO and HOMO orbitals to absorb light at all:


Finally, the arcane term “auto oxidation” that keeps getting thrown around isn’t a proper term used in organic chemistry. It’s from some era of field chemistry like natural products activity search, and the “auto” part means in air. It’s just air oxidation. There’s nothing “auto” about it, nothing involving two DMT molecules cooperating to swap electrons.

Here are some found images of DMT crystals that support the trace dye impurity claim, where white crystals grow out of yellow syrup, eventually filling the syrup with hard DMT needles:


Uniformly yellow crystals are even lower in impurity so the dye just gives a general rock candy effect rather than crashes out in dots or films. Permitted dye levels in sugar candies are typically 50mg/kg or an impurity level of a mere 0.005%. Color thus has little to do with practical purity levels since highly colored candy is regulated to be 99.995% pure, which is beyond even pharmaceutical grade up into analytical grade standards.
 

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Voidmatrix
#2 Posted : 6/21/2023 2:07:51 PM

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Haven't been able to read this at length, but appreciate your work and sharing your data. I've been in this camp for a while with regard to yellow DMT not being less pure than white.

I will say that I don't think calling out specific people here was necessary.

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Brennendes Wasser
#3 Posted : 6/21/2023 10:56:29 PM

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Quote:
Trace amounts of dimer that still afford 99.99% pure DMT can readily taint full DMT crystals, but never does the yellow go away upon melting or dissolution of the crystals. The only “yellow polymorph” mentioned in the classic paper on colored DMT was indeed cited as amorphous. They only characterized three colorless polymorphs, discarding the waxy solidified yellow mass.


Indeed just minimum amounts will already create the strong coloration. I tried to provoke the evolution of Dimers here and all I could analyze was still mostly the base substance. Of course NMR is no method for trace analysis, but it showed that even strong oxidizing and/or pH manipulation environments for days were not enough to produce a reasonable level of those. Seems that in practice it is luckily not a problem, only causing cosmetic effects. Still I had times when the early oiled-out fraction causes DMT precipitation to dissolve into this liquid and making me get less beautiful crystals ...
 
AbsolutelyPureDMT
#4 Posted : 6/22/2023 6:20:46 PM

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Here is a predicted NMR spectrum of my candidate for DMT oxidation dimer:

http://www.cheminfo.org/...1H_Prediction/index.html



The MOL file to recreate this is:

CN(C)CCc3c(c2[nH]c1ccccc1c2CCN(C)C)[nH]c4ccccc34
JME 2013-09-15 Thu Jun 22 12:54:18 GMT-400 2023

28 31 0 0 0 0 0 0 0 0999 V2000
5.5043 0.0000 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
3.1981 0.7493 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
5.0542 10.2541 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
7.3604 9.5048 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
10.5585 5.8271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
0.0000 4.4271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
10.5585 4.4271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
0.0000 5.8271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
9.3461 6.5271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
1.2124 3.7271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
9.3461 3.7271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
1.2124 6.5271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
6.3695 2.6630 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
4.1890 7.5912 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
5.0001 2.3719 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
5.5584 7.8822 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
6.8021 6.2597 0.0000 N 0 0 0 0 0 0 0 0 0 0 0 0
3.7564 3.9944 0.0000 N 0 0 0 0 0 0 0 0 0 0 0 0
6.8021 3.9944 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
3.7564 6.2597 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
5.9792 5.1271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
4.5792 5.1271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
8.1336 5.8271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
2.4249 4.4271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
8.1336 4.4271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
2.4249 5.8271 0.0000 C 0 0 0 0 0 0 0 0 0 0 0 0
4.5675 1.0404 0.0000 N 0 0 0 0 0 0 0 0 0 0 0 0
5.9910 9.2137 0.0000 N 0 0 0 0 0 0 0 0 0 0 0 0
1 27 1 0 0 0 0
2 27 1 0 0 0 0
3 28 1 0 0 0 0
4 28 1 0 0 0 0
5 7 2 0 0 0 0
5 9 1 0 0 0 0
6 8 2 0 0 0 0
6 10 1 0 0 0 0
7 11 1 0 0 0 0
8 12 1 0 0 0 0
9 23 2 0 0 0 0
10 24 2 0 0 0 0
11 25 2 0 0 0 0
12 26 2 0 0 0 0
13 15 1 0 0 0 0
13 19 1 0 0 0 0
14 16 1 0 0 0 0
14 20 1 0 0 0 0
15 27 1 0 0 0 0
16 28 1 0 0 0 0
17 21 1 0 0 0 0
17 23 1 0 0 0 0
18 22 1 0 0 0 0
18 24 1 0 0 0 0
19 21 2 0 0 0 0
19 25 1 0 0 0 0
20 22 2 0 0 0 0
20 26 1 0 0 0 0
21 22 1 0 0 0 0
23 25 1 0 0 0 0
24 26 1 0 0 0 0
M END
 
Brennendes Wasser
#5 Posted : 6/22/2023 10:19:13 PM

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I tried to find this in my NMR but found nothing Embarrased



C5 (as labelled by the software) still at 1. (~ 1.06)

So I'm also pretty sure it is a go-to product of any form of DMT oligomerization so pretty sure traces of this existed in my sample, but still below sensitivity for NMR. That was really strange, as those conditions were really forcing possible conjugations I thought. No solvent AKA highest concentration possible, heating to liquify and increase molecular motion and also DBU is a strong base, not as strong as NaOH but should do the job. After all the time I waited I dont think longer reaction time would help. I guess equilibrium for all possible oligomer formation is simply pretty much on the monomer side. If true polymerization itself is only driven by a big enthalpy release and as DMT is not "designed" for this I guess we might never see this potential substance purified from a quantitative reaction and by eye?

Also I did not test acidic oligomerization as most members suggested the reaction might happen during the base step and both A/B and STB TEKs might form yellow crystals, while an acidic step is only performed during A/B. Maybe might be another chance with DMT @ 70 °C for like 2-3 days and added water-free acid like TFA. Confused

Another idea to confirm this mode of coupling could be 13C-NMR, but it seems it would just shift by 3 ppm (so basically 0 with C-NMR) and even if it would be more distinguishable, sensitivity issues would be even worse with 13C Sad Sad
 
AbsolutelyPureDMT
#6 Posted : 6/23/2023 3:29:42 AM

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The impurity can hide well within the broad peaks of DMT monomer, being so similar in proton environments with merely C2 missing one.
 
Brennendes Wasser
#7 Posted : 6/23/2023 7:19:49 PM

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Yes that's true so I would also really think a Dimer like this would be hiding here. But I just have NMR as a tool since some time, but would not even know which other analysis could confirm this specific dimer.

Benzyme also uploaded MS data with multiples of DMT mass. So technically also the benzene ring should react. But I also think that Dimer is the most prevalent of any possible oligomers. Reason is simply that I think only the indole ring is reactive if the tryptamine is non-substituted. It seems only with some Donor-substituent at the Ring like Psilocin the reactivity / chance for oligomerization there is increased significantly.
 
Exitwound
#8 Posted : 6/24/2023 8:06:40 AM

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That’s what it feels when entities talk to me, they make sense overall, yet somehow it is all gibberish Big grin

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Loveall
#9 Posted : 6/24/2023 1:58:03 PM

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In my experience the oligomer properties are strongest closer to the plant and more noticable when a larger amount of DMT is extracted.

For example a cold naphtha pull will give white DMT, but leave a lot of yellow DMT behind.

I think that some DMT in the plant is naturally in oligomer form somehow. Not sure if it makes sense if it is indeed in salt form, but experimentally it would explain a few things (yellow dmt oil rate is max. near the plant during extractions + there is variability for different plant batches for same TEK/operator).

I have never done DMT synthesis, but I imagine they could also form there at varying degree depending on the synthesis conditions?

I think metal ions + heat break any natural dmt oligomers down, especially at 2M or so. Na+, more so K+, and even Zn++. The max ion tek may be doing this.

Also, FASA or benzoic acid salting from Toluene also seem to break down oligomers.

I could be wrong.
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tryptamine9
#10 Posted : 6/24/2023 9:44:34 PM

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I once had yellow tainted DMT and did a mini a/b using an excess of sulfuric acid.
The coloring went away and I had nice white crystals.
What peaked my attention was that all liquids also where colorless afterwards.
What might that imply?
 
benzyme
#11 Posted : 6/25/2023 1:12:26 AM

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there's no such thing as a "yellow polymorph", per se; the ochre color is attributed to autooxidation of pyrrole at the 3-position. The discoloration also occurs in tryptamine and indole.
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downwardsfromzero
#12 Posted : 6/26/2023 8:52:23 PM

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This is highly reminiscent of the oligomeric alkaloids in the psychotridine series.

Food for thought there that we see the oligomerisation occurring through the 3- and 7-positions on the indole ring; of course, enzymatic process will have been at play. We can see as well that - in the case of the particular monomer concerned - the 2-position is occupied from the cyclisation via the amine nitrogen.


One small point of order: it's incorrect to refer to harmine as being a carbazole - 'nearly' is not close enough. It's pretty rare to see betacarbolines referred to as azacarbazoles. Therefore it's best to stick with the established nomenclature.

The putative reaction scheme seems rather spurious in that you moot an acid-catalysed oligomerisation which would imply that the maximum amount of dimer would form by mixing solutions of equimolar amounts of DMT salt and DMT freebase. Have you (OP) tested this? It's also a bit disingenuous to use a synthesis reaction scheme from a rather different starting material which uses an iridium complex as a catalyst to somehow underpin the argument for the oxidative formation of DMT dimer. All it does is illustrate that 2,2'-bisindoles can and do exist.

Have you examined the HOMO and LUMO of the one-electron oxidation product of DMT? Such radical cations can be expected to display intense coloration.

Great that you've been thinking about this though - but a more conciliatory tone may work in your favour.




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