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Dry ice to precipitate NMT carbamate out of NP solvent for ACRB extract

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arcologist

arcologist

Rising Star
So I've been trying an ACRB extraction and I've got to the point where I can reliably get pure white crystals to freeze precipitate.

My method is STB with 60g NaOH/L, 4x pulls with heated naphtha, evaporate to goo, dissolve goo in acetone, convert to DMT/NMT fumarate with fumaric acid, settle and decant acetone (removing plant oils), redissolve fumarate goo in water, base with 20g/L NaOH, 1 or 2 room-temperature pulls with naphtha, leaving most NMT behind, freeze precipitate for 12+ hours.

However, these crystals turn to goo at room temperature, probably due to some small amount of NMT present in them. I've tried various methods of drying/raising the temperature slowly, but nothing has worked.

I saw a paper posted here (attached) from 1964 which claims that bubbling CO2 through a NP-solvent solution of secondary and tertiary amines will cause the secondary amine-carbamate to precipitate. Since NMT is a secondary amine and DMT is a tertiary amine, it should be possible to separate them in this manner.

My idea is too dissolve my NMT/DMT crystal goo in a non-polar solvent (naphtha or maybe xylene?), then put a small piece of dry ice (solid CO2) into the solution. The dry ice will sublime, creating CO2 bubbles that should run the above reaction. It will eventually all sublime, leaving your solvent ready to be filtered to remove the NMT carbamate.

Does anyone see any potential problems with this experiment? It seems like the easiest way to generate controlled amounts of CO2 and hopefully separate the rest of the NMT.

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Update: 10/25/2013

I have had the chance to try this technique in a few different permutations with moderate to good success. Some other users have reported some moderate success with this method, but most with low yields. I have had yields of around 0.7%, extracting from the same source of bark each time.

So far, I have had the best results using xylene for the dry ice reaction. The reason for this is because only the NMT carbamate precipitates using xylene, but with naphtha, much of the DMT precipitates due to the drop in temperature caused by the dry ice. This requires a hot water bath to raise the temperature of the naphtha enough to redissolve the DMT (leaving the NMT insoluble). Using naphtha may reduce the final yield of DMT because some solid DMT gets trapped in the NMT carbamate residue.

It is best to collect all pulls and to add dry ice to all of them together, but to no more than 250-400ml of solvent at a time. More liquid than that and there is the chance that the CO2 doesn't react with all of the NMT.

Images:
1. NMT Carbamate precipitates using dry ice from xylene
2. NMT Carbamate/DMT freebase precipitated from naphtha, before heat bath.
 

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I like your style. Being able to precipitate out the NMT with dry ice would be a cool trick.

I can't wait until someone with the chemistry knowledge chimes in.

My method is STB with 60g NaOH/L, 4x pulls with heated naphtha, evaporate to goo, dissolve goo in acetone, convert to DMT/NMT fumarate with fumaric acid, settle and decant acetone (removing plant oils), redissolve fumarate goo in water, base with 20g/L NaOH, 1 or 2 room-temperature pulls with naphtha, leaving most NMT behind, freeze precipitate for 12+ hours.
Click to expand...

Quite the process! How much material do you tend to lose after you leave the NMT behind?
 
alert said:
Quite the process! How much material do you tend to lose after you leave the NMT behind?
Click to expand...

It seems like about half of the material is left behind when doing the final naphtha pulls, it remains as an off-white/yellow goo that rises to the top of the water layer. I didn't weigh the material at any stage until the end of the process, but I can comment on total yield. My test batch of 100g ACRB yielded 1.05g of white DMT crystals that turned to goo, weighed by evaporating in acetone onto mullein, subtracting weight of mullein. I tested it tonight and it seems to be about as potent as a mimosa extract. I think that's a decent yield, I was pleased with the results.
 
I got some dry ice and put a small piece (<2cm^3) into a naphtha solution of NMT/DMT goo. Immediately, the solution seemed to violently boil as the dry ice sublimed (be careful, use a container with high sides). Within 20 seconds it was all gone and a large amount of white precipitate remained.

I didn't think about the change in temperature of the solution, so much of the DMT must have crashed out as the temperature was quickly lowered toward -79C. After a warm water bath, most of the solids went back into solution, leaving a small amount of clumpy off-white solid that stuck to the bottom, which I assume is NMT carbamate.

I filtered out the solids and am now freeze-precipitating the naphtha to see if I can get nice sturdy crystals this time.

If this works as expected, I could definitely see a dry-ice step being added to ACRB teks after doing the initial pulls. It's an almost instant reaction and hopefully will allow people to separate their NMT from DMT.
 
If it's a principle that simply depends on it being a secondary or tertiary tryptamine, then yes you could separate it too.

Notice though, that carbamate is not simply a salt form of the substance or something like that, it's a totally different substance, so if you're looking to use the NMT/5-MeO-NMT or whatever, then this is not a good way (unless you look into the reduction of carbamate to the original compound, which would introduce other complications).

It makes me wonder why isn't it simply a carbonate salt being formed. Mescaline can be salted with CO2, and it's a primary amine, so why isn't it working on this case? Does it depend how CO2 is introduced, conditions of temperature/pressure or other catalysts?
 
According to the posted paper (column 2, line 55), the carbamated amines should be able to converted back to their original state by treatment with an alkali metal hydroxide (i.e. NaOH), so you would just have to base the alkaloids (which seem to only be soluble in acidic water, based on my tests of the NMT cabamate), then pull again with an NP solvent to recover them.
 
Maybe the mescaline reacts more readily with the carbonic acid formed by CO2 than with the CO2 directly. No idea why that could be though.
 
endlessness said:
It makes me wonder why isn't it simply a carbonate salt being formed. Mescaline can be salted with CO2, and it's a primary amine, so why isn't it working on this case? Does it depend how CO2 is introduced, conditions of temperature/pressure or other catalysts?
Click to expand...
CO2 needs to react with water in order to get converted to carbonate and subsequently salt mescaline.

Just introducing CO2 obviously won't do any salting :)
 
The patent you posted is neat. Please be aware that patents are not sources of reliable peer reviewed information. They are often concealing in nature. This however is a well documented effect (carbamate formation).

It's an exothermic reaction excess dry ice is a good idea. The only issue I see with this is potentially a loss of yield (as in DMT carbamate formation). Carbamate formation is a kinetically slow at STP and low concentrations of CO2. It is ideal to use dry ice as described above.

The issue is dimethyl tryptamine isn't too too sterically hindered as some of the examples in your patent seem to be. TLC would help make things more clear.
 
endlessness said:
In that thread, the original post is also an easy-work conversion to separate primary/secondary and tertiary amines, by using aspirin and alcohol.
Click to expand...

That is some MacGyver chemistry right there.
 
Great news! The freeze-precipitated crystals haven't turned to goo!

I had 2 bowls of material in the freezer - in one, which I only put dry ice in once, there was still some goo formation. The other was all crystals. I guess I should have put the dry ice in both 2 or 3 times in order to make sure all of the NMT was removed.

Unfortunately I don't have access to TLC to confirm that the NMT was removed, but I'll say that these results are as good as anything I've ever gotten from mimosa, so I'm very pleased. Interestingly, it doesn't have the same flowery smell that mimosa DMT would have, it has no smell at all. Edit - it does smell, but not like mimosa DMT or even the acacia goo. It is a kind of faint acrid chemical smell, somewhat like vaped spice. This is definitely some of the purest spice I've ever seen, shiny white crystalline powder and totally devoid of any waxiness.

I'm trying it again on a final xylene pull of my base soup to see if it's possible to do the same thing when there are other plant oil impurities in the solution. Update: it worked great, produced a ton of NMT carbamate (xylene picked up lots of NMT). I was afterwards able to precipitate nice white fumarate crystals from the xylene using FASA, plus a mystery red waxy alkaloid.
 

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Interesting, out of all the extractions I've ever done I've never came up with an odorless final product.

Great work you are doing!
 
Arcologist- way to go!
Your method of using dry ice to separate NMT/DMT is brilliant!
I have several batches of 'goo' that I will try.
Maybe 3x with the dry ice?
Thanks. I will forward any results here.

DP
 
Thanks! It really depends on how much NMT you're dealing with, but 2 or 3 times with a 2 cm^3 size chunk seems to be more than enough for mostly DMT goo. I tried it on some xylene pulls (which had way more NMT) and it took a few more times to get it all to precipitate.

Let us know if you have any success!
 
Woah, now this is neat. Ya got me wanting to extract DMT I don't need 😁

Now, is the NMT discarded entirely, or can it be saved and used on its own? I don't fully understand the chemistry involved, as it sounds like you're not simply forming a salt using the CO2, but rather a carbamate, whatever a carbamate may be.
 
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