Experiment #2 also done now. But this is now much cooler than the theoretical talks with no experiments, so it is pasted at first position into the first post. So click back to Page 1 to see the full text.

In short:

Radically induced Polymerization seems to produce the SAME reaction pattern regarding positions of DMT to Polymerize and the SAME reaction ratio of non-reacted to reacted bonds.

That makes me think if there is

A) a saturation of reactivity where no more positions are likely to react per molecule (probably disfavored by steric hindrance)

B) a saturation of coupled C-C bonds after which the polymerization degree does not rise any further (probably disfavored by entropy)

N-Oxide formation in both cases was also pretty similar ~ 2,5 %. If these are built into the Polymer or just stick around inbetween we won't know, as we also cant extract them as monomeric molecules with Hexane. As reaction conditions were quite different regarding initiation/catalyzing system and time, this makes chances kind of high that the proposed Polymer structure from Experiment 1 is the one that was mostly retrieved in both cases.

At the end there is also a picture shown which is mapping the reactivity of DMT across the molecule regarding the results of this experiment, at least for Polymerization purposes. Now also posting here:



In conjugated systems you often share a reactivity across 1,3-positions or 1,5-positions and so on. In this case it is different for the 6-Ring as you can see. Reason is: if you draw the Mesomery that can be induced from the indolic N then if you delocalize the N-electron towards left position you will end up with a negative charge at position #8. If you delocalize the N-electron towards the upper position you will end up with a negative charge at position #11. This former rule seems the be overcome by the fact that the ring of the N is only 5-membered, so in total in DMT position #8 and #11 show the same reactivity pattern, even if the are conjugated in a 1,4-(para)-positioning.

So to conclude, the conditions which created those polymers are not exactly what we expect in an extraction or when vaporizing Spice. But I think it is still rather likely that reactivity patterns which are observed here should also give hints how the DMT molecule would behave in similar conditions and therefore would possibly create Polymers pretty similar or not too different from what I have drawn here.

Here as a summary of everything the proposed "average DMT-Polymer structure" that was retrieved from those experiments:



This structure is only valid if we assume that 1 DMT binds 2 new molecules. Also 3 (or with Position 9 / 10 even more) would be possible, but probably chance for creating these decreases dramatically. Therefore based on these experiments I may carefully assume that DMT Polymerization stops at the shown Hexamer with only minor chances of elongating the Polymer chain at the outermost positions #9 / #10.

As usual with Polymerization, there might be any kind of other isomers / wild combinations possible. But as any reaction will have a certain prefered pathway through minimizing energy barriers and thermodynamically most stable products, there should be at least a set of preferred patterns of Oligomers.

Sadly have to revise all both experiments Initial post is therefore corrected and just for sake of information the wrong one then attached above this post.

There was an error:

To get the total count of aromatic signals per 1 molecule it was important to normalize the whole spectrum to 1 signle molecule. Putting the NMe2-Peak to 6 at 2,23 ppm is wrong, because also N-Oxide is evolving and thus "1 molecule" is shared into X DMT and Y DMT-N-Oxide, which make up for a total of 1 molecule. This way the aromatic signals and the indolic NH can be analyzed pretty well.

But I mistook the signal at 2,50 ppm for the N-Oxide Which is actually DMSO. Instead N-Oxide is at ~ 3,15 ppm, but forgot. Now in both cases N-Oxide is much less. That also means that X for DMT is much higher and pretty close to 6. Now increasing this number it will also increase the aromatic signals + indolic NH integral. It's actually increasing so much, that you now get to an amount which is basically 1 for all single protons That would be a perfect indication that NOTHING actually happened. As this is now in accordance with the actual chemical shift, I have to strongly assume that the corrected version is correct ... and therefore no sign of polymerization took place.

Still the link to the old spectrum is given as a side comment, but that probably means no additional insight into possible DMT-Polymer structures.

Comes out quite weird that these *harsh conditions* seemed to make absolute 0 effect. Some decrease of indolic NH, but nothing else so still no information of how it could have reacted. At least this is somehow in accordance with any other result, which also never saw any reasonable evolution of N-Oxide or Polymers. But that makes me again wonder too much why whatever leftover I have in both cases does still not dissolve in boiling Heptane, if it really would be not pure freebase DMT?