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First Extraction Attempt & Pure H1-NMR of Product

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xChemDawgx

Rising Star
Hi all!

This is my first post on this site, but have spent the past few weeks pouring through yalls amazingly helpful resources. SWIM went ahead and ran his first extraction from 140 g of MHRB. The extraction tek that he decided to used was a hybrid of a a/b "salting" tek with hot heptane and finally DCM pulls. SWIM is a PhD Chemistry student right now and was able to have access to reagent grade chemicals and all the necessary glassware. Finally after 2 recrystallizations in hexanes and high-vac solvent removal, SWIM obtained 814 mg of high purity white crystalline spice and another 320 mg of more yellowish crystals. SWIM still has a few questions. Some people get yields of 1.5 g spice from like 50 g of bark. This yield seems to be over 100% given the spice content in dried root bark. Are they pulling other impurities out as well then? Also, are the yellowish batch of crystals SWIM isolated considered more "full spectrum" alkaloids?
Additionally, SWIM ran proton NMR on the isolated white powder and would like to post said spectrum for future reference. It looks pretty pure comparing chemical shifts and integrations from some papers SWIM found back from the 70's and 80's.
Just wanted to thank this community for all your advice here. Cheers!
 

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Welcome to the Nexus!

Thanks for sharing your results!

These two threads might be of your interest, if you haven't seen them yet:


I think a lot of the peer-review publications use ineffective extraction methods hence provide a lower total % than posted by some people in the underground. 3% is not likely but over 1% is definitely possible and reasonably common. There might be some variation in plant product and could also potentially depend if the rootbark's outer part was cleaned before grinding, supposing the inner bark has a higher alkaloid content.

Impurities might be present in some extracts but generally after such selective solvents like heptane/hexane the product is quite pure, even more so after re-x.

Did you run the NMR on the DCM pulls, or the yellow product too?

Be well!
 
WOW! These threads are whats up, thank you! Even have TLC analysis hah, that's awesome.
That's a good suggestion though, just for comparison sake, i'll plan on running NMR on the yellow crystals tomorrow and get back to ya. I actually combined the multiple heptane pulls and final DCM pull, with the plan to get as much out as possible and then purify after the extraction. The yellow isolate was from the more dense viscous "oil" which settled first, after heating up crude material in hexanes and allowing to cool to rt. I pipetted off the milky white layer and subjected that to recrystallization.
Thanks for the warm welcome also : )
 
okie,
was actually able to pull off another 240mg from the basified aq layer I had put aside. I found that it still wreaked of spice so did a couple more DCM pulls *Note: I found very nice separation, almost immediately in the sep funnel using heptane, where as emulsions persisted for hours from DCM pulls* and concentrated down the organic layers after using a large amount of sodium sulfate to remove emulsified aqueous layer contamination. re-x in hexanes, but didn't separate the dense yellow oils time. NMR of last crop was just as pure as the NMR of the small glassy shards I recrystallized from a earlier pulls. Im curious what these yellow alkaloids are then if spectra look practically the same... posted a couple pdfs of the spectra I took of the original crop yellow product that was asked about by endlessness, as well as the final 240 I pulled out as the last crop.
will be scaling up soon on 400g, I believe.
 

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Hey xChemDawgx,

Welcome! Thanks for sharing your experience with DMT extraction!

There will be a lot of variation between the "literature values" and the final yields. There is going to be some loss during each step. So, depending how many different approaches are applied, and the desired result (very pure isolate? "Full spectrum" etc etc), its not uncommon to fall outside of the literature values.

I'd imagine that the locality of trees and their environmental factors will play a role in the total alks that are produced by each tree.

Maybe perform an extraction efficiency analysis?

Take care!!
ACY
 
Heya ACY, yes I think an extraction efficiency analysis would be interesting. I might aliquot a few hundred mLs of basified aq. solution next time and run separate small scale extractions using a couple different organic solvents (id like to try Et2O or CHCl3, maybe toluene?) to see what is most efficient and provides the most pure product as well. thanks for you suggestion!
 
xChemDawgx said:
okie,
was actually able to pull off another 240mg from the basified aq layer I had put aside. I found that it still wreaked of spice so did a couple more DCM pulls *Note: I found very nice separation, almost immediately in the sep funnel using heptane, where as emulsions persisted for hours from DCM pulls* and concentrated down the organic layers after using a large amount of sodium sulfate to remove emulsified aqueous layer contamination. re-x in hexanes, but didn't separate the dense yellow oils time. NMR of last crop was just as pure as the NMR of the small glassy shards I recrystallized from a earlier pulls. Im curious what these yellow alkaloids are then if spectra look practically the same... posted a couple pdfs of the spectra I took of the original crop yellow product that was asked about by endlessness, as well as the final 240 I pulled out as the last crop.
will be scaling up soon on 400g, I believe.
Click to expand...

According to our tests, yellow is generally just dmt, hence the spectra, the thing is that dmt is polymorphic, so pure dmt can also be yellow and viscous oil.

Thanks for posting the files!
 
So I also included NMRs of quite impure samples and they still contain nearly 80 % DMT :? 😁 😁

My thoughts on this:

I dont think that the DMT itself produces that yellow colour by any polymorphic stuff but that this is just a really slight remainder of stuff from the aqueous solution.

It should normally be really black at pH 10+.

But if you dilute it extremely it will become brown and after a lot of time slightly yellowish.

This is basically a leftover of chemicals that produce the dark colour of your aqueous phase.

Also DMT itself gets brown upon heating and/or UV-exposure, but I dont think that yellow spice out of impure extractions are coloured by the same thing ... it should mostly just be a leftover from the pulling step.

So you will see: Even stuff that looks AWEFULL impure will show up as 70 %+ DMT in the NMR :? .

I am now preparing a sample of the aqueous phase itself to be thrown into NMR. It SHOULD look like all the Signals EXCEPT DMT of that *Impure Spice* Sample I measured some time ago.

Therefore I'm pretty sure that all those brownish stuff is just unuseful stuff, not something like *Full Spectra*.

Also all that other Signals together seem to belong to *boring molecules*, no aromatic signals nor carbonyles etc.

Therefore I highly doubt that there is any other Indol and/or psychoactive component at all present in pulls at ~ 70 °C+ extractions - or at least not in any relevant amounts if even NMR cannot measure it. :?
 
Brennendes Wasser said:
So I also included NMRs of quite impure samples and they still contain nearly 80 % DMT :? 😁 😁

My thoughts on this:

I dont think that the DMT itself produces that yellow colour by any polymorphic stuff but that this is just a really slight remainder of stuff from the aqueous solution.

It should normally be really black at pH 10+.

But if you dilute it extremely it will become brown and after a lot of time slightly yellowish.

This is basically a leftover of chemicals that produce the dark colour of your aqueous phase.

Also DMT itself gets brown upon heating and/or UV-exposure, but I dont think that yellow spice out of impure extractions are coloured by the same thing ... it should mostly just be a leftover from the pulling step.

So you will see: Even stuff that looks AWEFULL impure will show up as 70 %+ DMT in the NMR :? .

I am now preparing a sample of the aqueous phase itself to be thrown into NMR. It SHOULD look like all the Signals EXCEPT DMT of that *Impure Spice* Sample I measured some time ago.

Therefore I'm pretty sure that all those brownish stuff is just unuseful stuff, not something like *Full Spectra*.

Also all that other Signals together seem to belong to *boring molecules*, no aromatic signals nor carbonyles etc.

Therefore I highly doubt that there is any other Indol and/or psychoactive component at all present in pulls at ~ 70 °C+ extractions - or at least not in any relevant amounts if even NMR cannot measure it. :?
Click to expand...

Oh nice, yes actually endlessness recommended your thread to me earlier and I really really enjoyed your analysis :thumb_up:
also, yea suspect the yellow is some form of impurity left over from the highly basified aq pull. however I found that NMRs of the isolated dense dark yellow oil that settles upon the first steps of recrystallization were highly concentrated with spice and mildly pure at that. But, I still have not really experimented with it enough yet to draw and conclusions at this point. Additionally, I have only vaped the "purer looking" white crystals. so im not sure how the yellow ones smoke yet either.
 
xChemDawgx said:
Heya ACY, yes I think an extraction efficiency analysis would be interesting. I might aliquot a few hundred mLs of basified aq. solution next time and run separate small scale extractions using a couple different organic solvents (id like to try Et2O or CHCl3, maybe toluene?) to see what is most efficient and provides the most pure product as well. thanks for you suggestion!
Click to expand...

Good plan about the aliquot. :thumb_up:

The solvents you've mentioned will work great! Especially if you have the access to equipment to evaporate under reduced pressure, while reclaiming the solvent. I wish I still had access to a rotovap. Lol.

So, they are good if you have the equipment, but not so much for crystallization via freeze precipitation. Honestly, my favorite crystallization solvent is n-heptane. I've grown beautiful crystals from n-heptane. Then.... the local suppliers stopped carrying it and I didn't want to take chems from my lab (at the uni), nor did I want to order it online - so I had to settle for a naphtha blend. Oh well. We can't get it all.

N-heptane is pretty selective, so it will pull less "junk" than toluene. I have not worked with Et2O on bark - so, no comment. And i have a bottle of CHCl3 packed up and waiting to be used on an extraction (at some point.)

I've really only used toluene, naphtha, n-heptane, d-limonene, sunflower oil, acetone(different concept than an STB), and isopropyl.


But, it's always nice to experiment!

Keep us posted.


Take care,
ACY



Ohhh, another thought. Do you have access to GC-MS or HPLC? If so... you could take crude aliquot from each of the different solvents and see what is to be seen. (Are there other impurities? What is the retention time when DMT elutes? Can a calibration curve be generated based on the solvent that is most selective?
 
Yes DCM will almost surely induce the need for a recrystallization : S

Also I think I tried Ether once, but it pulled the most junk I experienced EVER out of the bark.

Also one should not forget to do the regular NaCl / Brine-wash afterwards as the Ether could still contain up to 5 % water, resulting in a goo upon evaporation. If one would evaporate it in a rotavap to get rid of the water without ether wash, it is likely that your crystals won't be that nice and who does not like crispy crystals 😁 😁 .

I think it is highly debatable if using DCM or Et2O would be worth it pulling more spice as it also drags other crap by an extreme amount.

Normally no problem because of recrystallization, but the brown stuff that is left over at the bottom of the naphtha acts like a different phase and there will be an equilibrium of spice between those 2 phases, so you may not get everything out : S

But I also just prefer using Naphtha instead as I do not have a rotavap now so ... maybe this is the reason :!: . But strong Solvents seem to always produce oils because of impurities and therefore if one is about to handle the freebase, it is simply better to start with heptane from the beginning. Also because I even doubt that there is anything other worthy inside that bark, which is released at meaningful amounts during an acidic cook ... :( Juremamine will never be extracted with a home TEK and still nobody ever tried it to state it is even active - and stuff.
 
hmmmm, I think you bring up some interesting points here, Brennendes Wasser. For my first extraction attempt here I used a heavy salting of aq acidic solution after multiple cooks and strains (through Buchner funnel first then cheese cloth) and finally following basification with conc NaOH.
Also, are you referring to STB teks when you're directly extracting with these diff solvents from broken down basified bark?
I have access to anhydrous ethyl ether as well so maybe that might be a go to for extraction sake, good call. I think perhaps I should focus on heptane and maybe DCM (or CHCl3) pulls to tinker with just to keep it simpler. While I'd like to experiment with other solvents I think you have a point that just straight n-heptane would be the ideal extraction solvent just based on the reading that I've done. also again, have you been drying your organic pulls with anhydrous sodium or mag sulfate? I found that clumped together all the brown aq based impurities and allowed for efficient decanting/pipetting of the organic layer.
I do wonder tho if the solvent selection would vary in efficiency between different procedure, from STB to a/b.
Thanks for your input and perspective here though ;)
 
excuse me for being blatant, but as a phd student shouldn't this sort of thing be routine for you? Don't you do organic extractions every day? I must spend 6 hours a day doing routine extractions.

Fortunately DMT is one of the easiest compounds to purify that i've ever worked with... Once you realize boiling hexanes re-crystallization gives ultra pure crystals consistently, there no need to waste time with anything else. Rarely do compounds have such a simple method for purification that works on even the crudest of materials. On top of that extracting from MHRB, even with DCM, has always given me material pure enough that it could be directly salted with FASA to give a crystalline product even without hexane recrystallization. I normally would recrystallize the fumarates in isopropanol.

My guess for why people report very high yields, if the bark isn't already very high content, that they don't wait for the crystals to dry fully before weighing them. I've seen DMT hold onto grams of hexanes for more than 24 hours in open air, and the hexane peaks are almost always visible in proton NMR.
 
Mindlusion said:
excuse me for being blatant, but as a phd student shouldn't this sort of thing be routine for you? Don't you do organic extractions every day? I must spend 6 hours a day doing routine extractions.

Fortunately DMT is one of the easiest compounds to purify that i've ever worked with... Once you realize boiling hexanes re-crystallization gives ultra pure crystals consistently, there no need to waste time with anything else. Rarely do compounds have such a simple method for purification that works on even the crudest of materials. On top of that extracting from MHRB, even with DCM, has always given me material pure enough that it could be directly salted with FASA to give a crystalline product even without hexane recrystallization. I normally would recrystallize the fumarates in isopropanol.

My guess for why people report very high yields, if the bark isn't already very high content, that they don't wait for the crystals to dry fully before weighing them. I've seen DMT hold onto grams of hexanes for more than 24 hours in open air, and the hexane peaks are almost always visible in proton NMR.
Click to expand...

>< these types of acid/base extractions are quite familiar to me as I have done dozens of unique work ups similar. Its interesting to note that working with crude material to pure isolate is much different from starting with reagent grade Aldrich ordered starting materials for any synthetic organic procedure.
I think i should probs stop posting on my work here though, Im not in all honesty sure how discrete I should be with these experiments moving forward.
Thank you all for the invaluable info, I am in your debt and just wanted to contribute back : ) cheers!
 
xChemDawgx said:
Mindlusion said:
excuse me for being blatant, but as a phd student shouldn't this sort of thing be routine for you? Don't you do organic extractions every day? I must spend 6 hours a day doing routine extractions.

Fortunately DMT is one of the easiest compounds to purify that i've ever worked with... Once you realize boiling hexanes re-crystallization gives ultra pure crystals consistently, there no need to waste time with anything else. Rarely do compounds have such a simple method for purification that works on even the crudest of materials. On top of that extracting from MHRB, even with DCM, has always given me material pure enough that it could be directly salted with FASA to give a crystalline product even without hexane recrystallization. I normally would recrystallize the fumarates in isopropanol.

My guess for why people report very high yields, if the bark isn't already very high content, that they don't wait for the crystals to dry fully before weighing them. I've seen DMT hold onto grams of hexanes for more than 24 hours in open air, and the hexane peaks are almost always visible in proton NMR.
Click to expand...

>< these types of acid/base extractions are quite familiar to me as I have done dozens of unique work ups similar. Its interesting to note that working with crude material to pure isolate is much different from starting with reagent grade Aldrich ordered starting materials for any synthetic organic procedure.
I think i should probs stop posting on my work here though, Im not in all honesty sure how discrete I should be with these experiments moving forward.
Thank you all for the invaluable info, I am in your debt and just wanted to contribute back : ) cheers!
Click to expand...

Yeah, it is different. Once you learn the few tricks its ultra simple. Soak up all the valuable information on this site hehe. And yes, I think some discretion would be wise.
 
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