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BLAB & oxides from old bark

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Rising Star
I've a lot of old bark that doesn't yield aything via traditional STB other than a lot of oily liquid/goo when pulled using Toluene/Xylene. I reckon this is because the dmt has oxidised & is no longer pulled out by naphta.

I'm just wondering how effective BLAB is at pulling out dmt oxides from old bark (as fumarate) and whether this can be converted via the standard BLAB method into freebase as a solid?
 
I haven't extracted from that bark in a while, last few times I tried it I tried recrystallisation with Heptane (no success) & did Heptane/Naphta pulls before the Xylene, with the Heptane/Naphta yielding nothing. I think there may've been a very thin insubstantial film when evaporated but nothing on freeze precip & nothing really useful on evap till I tried Xylene/Toluene.
I'm sure that its the age of the bark as I'd had previous success with bark from that same batch.
 
xlogp-wise I think limonene should pull n-oxides. If you salt with FASW they should migrate to your acqueous layer and you should have them with your fumarates. To convert to freebase you could try the zinc reduction step.

when you say you tried to recrystallize the goo, what happened? nothing migrated to the naphtha? was it warm? did you weigh the goo? Is it possible you used too much naphtha and hence it didnt freeze precip?
 
Thanks Endlessness. Just to clarify
oxides should be pulled into the Limonene, then dissolve fumaric acid in water to get FASW (hadn't come across this before), add FASW to Limonene and agitate - say 50ml FASW, 3 or 4 times.
Will the FASW form an emulsion when agitated? do I need to stir/roll gently or can I shake the hell out of it?

Drain off FASW & evaporate.

Never tried Zinc reduction before - I was hoping to avoid needing to do this, but I'll look into it. Out of interest is there a reason the BLAB steps of FASI >fumarates >sodium carbonate > freebase won't work?

It was a while ago since I used that bark so I can't remember many details, I'd've used heated heptane as I tend to for re-crystallisation. Don't think I weighed the goo but I'll check my notes. From memory there was very little to scrape & weigh though & nothing crystalised out either from initial freeze precip or re-crystalisation of evap.
 
I've read up on the zinc reduction, looks simpler than I'd thought it would be. Take the fumarate, in acidified water, and add Zinc powder, shake or mix for 2 hours, filter thoroughly, basify, pull with solvent & freeze precipitate.
Will the presence of the dissolved fumaric acid in the water cause any issues with Zinc reduction? I suspect it'll be no different to using hydrochloric acid or citric acid and would be destroyed by the basification.
 
Your description of FASW is right.. I dont remember any emulsions ever forming for too long, but anyways might as well just stir strongly instead of shake, since the salting will be effective in any case.

You can try the FASI-fumarates-sodium carb freebase thing, but if its really n-oxide, the oxygen wont be stripped from it in the process, so I dont think it will crystalize (if you do the water crystallization), but it would come across if you do the IPA/acetone pulls on sodium carb/fumarate paste, but it might be more oily results.

Im not sure if the zinc reducton without a strong acid will work to be honest. Talking to myd on the forum he pointed out the necessity of h+ ions for the reduction to work, so maybe not using a strong acid will not work.. but I dont think anybody tried it yet with another acid so you would be pioneering this if you try it out. I suggest dividing it in 2, one where you do the zinc and one where you dont, to see if it really made a difference.

Good luck and keep us informed!
 
Thanks Endlessness, I'm going to sit down & work out my steps for doing this. I'll let you know results.

Ice House said:
Just curious... How old is your bark? I've done extractions on 3yrs + bark that still yeilded a solid 1%+.
Click to expand...

I think it must be about 3 yaers old by now. Last tried it last year with no success.
 
Ok, I've had a lot on in the past month & haven't been able to try this. I'm going to be out of town over the next month too but I figure I'd better get this process started. I've already run a BLAB extraction on 158g of the old MHRB, using scaled down standard volumes (300ml vinegar, 18g lye, 700ml water and 242ml of Limonene). So this is my plan. I've got 242ml of Limonene and will split this into 2 lots of 121ml.

Batch 1) will get the usual BLAB treatment of FASI >Fumarates + Sodium Carbonate > Freebase.
Batch 2) will salt with HCL acid & water, pulling the DMT & oxides into the acid water, water will be seperated & zinc added, mixed, filtered, basified, pulled with heptane & freeze precipitated to yield Freebase.

I expect this to take a bit of time but I'll let you know progress.
 
Process is now underway:
1) I've added FASI, there's a shimmery quality to the limonene when added but only very very faint clouds form & I doubt if much'll be recovered this way at all.
2) I've mixed 90ml water & 10m 5M Hydrochloric acid. This 100ml was added to the limonene. This'll be gently rolled, seperated then I'll do another 2 lots of 50ml & combine.
 
No change to 1)
2) have used & seperated an additional 2 lots of 50ml HCL water. I've now combined this HCL water - hopefully containing DMT & oxides - and added 10g of Zinc powder to it. It bubbles up a bit, releases a gas and a sort of hydrogenny/rotten eggy smell. I'm going to continue to agitate this then filter it.
 
I've now filtered 2) and added 5g of Lye, which turns out to be more than's needed as its gone to Ph 11 and turned milky white. Shouldn't affect a Heptane extraction though (I hope) & I'm going to do this next.
 
Things have gotten a bit more complicated. I've pulled 2 50ml lots of heptane through the miky white base water and lets another 50ml in with it overnight to settle an emulsion. Looking at it this morning its formed into 3 distinct layers. Milky white - a thick clear but slightly darker colour layer - and the clear heptane on the top. I'll post a picture later, but I wasn't expecting this.

Do you have any ideas Endlessness?

Also the 100ml of Heptane was put in the freezer overnight to give me an idea if anything's pulled out. No crystals have formed.
I've got 2 theories A)The Ph 11 is too high &the fact the water's gone white has prevented DMT from being pulled into the Heptane. Somehow.
B) Bark was bad after all.
 
P3310003.jpg
 
pH 11 might be too low, not too high. Higher pH = better for DMT moving to non-polar layer. I would add more base and see if anything changes. Also using the typical emulsion-removing techniques in the FAQ.

If nothing changes, I would separate getting the top 2 layers, then I would salt them out using vinegar, and then I would re-base and re-extract.

Good luck!
 
I tried adding extra base, but no change - Heptane pulled nothing out.
I tried separating the middle, clear water, layer. I've got this seperate from the heptane & white bottom layer (which has been kept). I've added vinegar to acidify - it takes a LOT of vinegar. After adding about 200ml (approx) of vinegar the base water/vinegar mix turned white.
I really don't know chemically what's going on here. The colour changes don't make sense to me. There should only be dmt & related mimosa bark alkaloids in this mix (& HCL) so I don't see how basification & acidification is resulting in the white colour change & the layer separation.

I'll keep an eye on it & report - but I'm not going to be able to do much over the next few weeks as I'm going to be away from home.
 
A few interesting developments. The vinegar I added has made very little difference to the PH, its still highly basic at ~Ph 11. I've run out of vinegar so can't acidify it more without using HCL or similar, which I'm reluctant to do as HCL was used in the initial acid/base & I don't want to risk repeting the same result.

The white has seperated again - white layer on bottom, clear on top. Still puzzling to me - why would the same reaction occur on the addition of acid as occurred with addition of base?

Much better news though - there is DMT present. I used a small sep funnel & beaker to seperate the layers and residue of the white layer was left in both. Now this has dried and there's a very familiar smell. So the DMT has ended up in the white layer (may be some in the clear layer too of course) - I have no idea what else's in there but I'd guess lots of Lye.

I'm tempted to evap all the white layer and mix in heptane to get DMT to dissolve & leave the lye but I'm concerned that'd just allow dmt-oxides to form again during the evap. Other option seems to be just mix the white layer with heptane - but for some reason that didn't work previously as the heptane layer from the pic above didn't pull out any dmt.

Any thoughts Endlessness?
 
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