I've analyzed the reddish goo from a recent experiment, which looks identical to some of the resinous leftovers from MHRB extractions. It isn't very soluble in hexane, cyclohexane, or ethyl acetate. Only DCM. And it doesn't readily crystallize.

What is it?

It is possibly polymers of DMT. The higher mass spectra have a difference of exactly 188 m/z, indicating coupling may have occurred during the extraction process.

How could I recover pure DMT? Perform A/B, or FASI/FASA/FASW.
I'm experimenting with tartaric acid, it has similar pKa's as fumaric.

From a synth, I suppose? Or is it sourced from a plant material?

Also, what are the other peaks there?

Kind of goo trouble in extraction, this might be related.
History:
STB powdered mhrb soaked for few weeks in lye water;
Pulled with toluene;
Toluene salted with HCL-water;
The acidic phase got based with lye-water;
Pulled this based liquid with heptane.

Basing the salted mini a/b liquid with lye, it formed nice thick white milk, but very soon a lot of this milk started to make the yellow/orange goo in the separation funnel and sticking to the sides. This made the milk less thick white. No pull was done yet!
Doing the pulls with heptane it did not pick up the goo.
The picture in attachment is the lye-based mini a/b that has been pulled with heptane twice (hence less white), the pull heptane is already separated.

I've had goo like that before but never that much.
In the past, very well heated (warning doing that!!!) naphtha could pick up all goo still, I'll see if it works now too and come back with that. At least this could separate the goo from the lye-water. By freezing and poring off the naphtha, the yellow oily residue got dried over months and eventually got rubber-ish harder yet flexible, very useful for pharma sessions though.

If that goo is re-storable as non-goo spice, would be nice to know a trick for that.

The goo is dead and no heated naphtha was used to pick it up.

Instead, after pulling the first mini a/b, then re-acidified the backwash {the based liquid + goo} until everything was dissolved again (took some effort to dissolve the goo but it worked nice), then re-base, 1 pull with 25ml heptane, repeat redissolving....
After each time basing, less goo formed, after 5 cycles of this all goo was out. I think it took 1 (maybe 2?) hour all together, the separations are lightning fast and no emulsions even when shaking very hard.

If there is a polymerisation or whatever formed the goo initially, by sequentially redissolving and rebasing it seems some former goo decides to freebase differently and more to our liking. This is a one off experiment though.

Maybe the backwash volume was too concentrated initially, promoting goo forming? In the 5x sequence the concentration is dropping gradually.
Also the salt content (ion strength) is rising gradually by each of the acid-base shiftings.

Anyway... happytimes

'twas from a synth. The other peaks may be adducts, from residual dcm.

Recrystallized product from my initial run gave only a single large peak around 189 m/z, m.p. 66-68 C, with a fragment around 144. <- that was from fluffy, off-white dmt free base crystals.

regardless of the method, the polymerization somehow occurs in the solvent itself...a supersaturated solution. I've never seen an extraction that didn't have goo in it.

is it possible to be a by-product to the reaction of DMT with DCM?

based on the spectra, I’d have to say no. There is no indication any chlorination side-reactions occurred, but I only ran it in full MS mode, not MS-MS.

Benzyme, have you chosen a column and mobile phase on your lcms that runs quaternary amine salts?
If not, you're not going to see the product of dcm and dmt.
It will be stuck at the front of your column or in your injection port.
I'm guessing your already know this and have taken it into account.

benzyme, this is very interesting.

Any more thoughts on what is happening? Are bonds inside the DMT breaking to form bonds with other DMT molecules? Which specific bonds could they be? Are C-H bonds being replaced by C-C? Attached is a paper saying that indole can do this at, for example, carbon position 2 (if I understand the paper). C3 is also mentioned as a potential site, but for DMT that is occupied. Below is a picture of a possible 2-2 dimer mentioned in the paper. Of course, the situation for DMT could be very different.

Or could C=C bonds in DMT be turning into -C-C- "sites" that can attach to other such sites?

nope.
Standard stuff.. Thermo Hypersil AQ (C1, and 0.1% formic acid in H2O to 100% ACN in 5 min.

Maybe thoroughly dissolving in acid can break any polymerization bonds over time?

I got some red goo that formed when DMT was left in a jar for a couple years. It is still active upon vaporizing, so heat may also help break these proposed polymer bonds.

Perhaps boiling in acidic solution for a couple hours may loosen things up. After that make alkaline and pull. I can test this out if there is interest.

Edit: Attaching a picture of the red gooey stuff. Two years ago it was fluffy and only had a hint of yellow.

I don’t think it’s occurring at any carbons, but rather at the amines. Further complicating this is the fact that this may also occur at the ion source; it’s been noticed in ITMS before. I’ll investigate further with highly resolved crystals, and more resin.
I need to figure out what the high mass compound is, that has a DMT molecule attached.

note: in the method used, there was no acid nor base involved, only 0.1% formic acid in the mobile phase.
no polymerization occurred at the ion source with recrystalized dmt.

yes, exactly. That’s why I’m converting with tartaric acid, to hydrolyze the polymers.

on the right is the polymerized dmt, on the left is a sample of it crashed out with TASA:W; ~ 60:40 acetone:water.
The background is the stock sol'n (TASA), with more converted product. There is no sol'n in the vial on the right, the sides are covered in polymer. I'm waiting on some fumaric acid to convert that, and will compare to tartrate salts.

The goo was dead, but resurrected during the freezing phase.

As I wrote the re-acidification/basing trick worked to get the goo picked up by heptane, the loaded heptane was nicely white clouded and no goo there at the bottom at all. One would expect to have only white shards from that.
But during freezing all goo resurrected as if it remembered that kind of potential, strange.

77% of end weight was pretty hard goo, the rest white shards.

^^ reason for so much goo-state might be spice sitting way too long in every phase, in the base, in the pulls, in the backwash, it all sat there sometimes even for days!

This experience might motivate for boiling bark in acid-water instead of stb. The acid cooks might (?) reset the spice polymorph-memory leading to more white shards, but I'm out on a limb here.
Or in general not let it sit for so long in the different stages.
Perhaps it is also already programmed in the bark how it will end likely, this batch has led to much more yellow that usual in more occasions.

I don't know how much of this goo state is relevant to polymerisation mechanism, I was just thinking it might be.

I was pondering the same. Crystallization, of course, is a result of uniform, homogeneous arrangement of the crystal lattice. This would be disrupted by mixed conformations.

under UV-A light (365nm), the polymerized resin glows yellowish. DMT glows bright teal. What that suggests is that the resin has a structure with more extensive pi-bond conjugation (meaning: more double-bonds).

I've done more tests on this topic trying to reproduce some of Jees' work.

After plant MHRB extraction, starting with what is supposedly relatively pure DMT:

1) Strong water base with high ionic strength (NaOH and NaCl) forms white milk first, then red goo on top (same as Jees). If the top layer of goo is removed, the basic water has no DMT in it (based on subsequent Naphtha pull and freeze). This top layer of red goo does dissolve into warm naphtha, but it clouds and precipitates as goo pretty quickly (not crystals) even before going into he freezer. This is different than Jees' result where the red stuff that separated out during the basing step did not go into naphtha (not sure if he tried warm Naphtha or if his goo was different).

2) Red goo from Naphtha was dissolved resolved in vinegar, citric acid and vitamin C and left to stir overnight. Basing that at low ionic strength and pulling with Naphtha resulted in some goo and a lot of crystals being formed during the freeze step. The goo was at the bottom of the jar, indicating it precipitated first.

Speculation based on these observations: I think this is consistent with red goo being DMT in some kind of condensed form. Seems it can form in the basic step at high pH and ionic strength. It clouds and precipitates first from Naphtha (less soluble) as an orange goo. It can be broken up in an acid step to some degree over time (perhaps heat is better than stirring).

One question I have is, Has anyone tried an extended Naphtha boil on the goo? I wonder if that will revert it back to an "uncondensed" form that precipitates as white rystals. If yes, the re-X may be performing this function already and a simple longer naphtha boil could be beneficial (instead of repeating re-X). Will try this out on red goo if there is no answer. Idea would be,

Goo -> add naptha -> boil in Naphtha for extended time -> freeze -> White crystals?

Thanks for testing

My goo was able to be picked up by naphtha, but very reluctantly, yet giving it several washes with tiny shots of very hot naphtha it all went into the naphtha eventually. I think we are on par with that.

I've never given it a thorough naphtha boil however. I always thought that this would be detrimental for white flakes forming and more goo promoting (where did I got that idea from??), but you might be right that it might be the other way around. To be tested.

Differences with you:

- I've never given the (in slight acid) dissolved goo a deep pH treatment, I thought dissolved is dissolved period. You used much more acid than I did with all that citric acid and vitC.
My dissolved-only-no-more method was unable to deep PH treat the goo.

- I usually don't use NaCl in a backwash pull at all, so if goo formed it likely did that under the high pH of lye only. Also in the first pulls on the bark soup I'm very prudent with NaCl for no special reason actually.

Remark:
last time I gave the goo a zink reduction step (though I suspected no dmt-oxide) but just to see what followed. I got like 50% less goo, so it worked a bit. It was an overload of vinegar power with several times dripping in glacial acetic acid while many hours in the stirrer.
So perhaps I conducted a better 'deeper' pH treatment with no real zink benefit, maybe same happened without the zink at all? Kudos to the glacial acetic acid?

Tempting to drag out the muriatic acid next time to give it a real deep pH treatment.
That, and the naphtha boil session are to be tested separately from each other.

Thanks for the efforts, I'm glad to feel a bit simulated