Not too best results, things must get better.

What was the volume please of the vinegar liquid containing the 1.3 grams, so right before you started adding ammonia? I wonder if a too low volume is the main parameter for goo forming.

Second: was it a hard sticking goo, or just powder that comes easily loose from the spoon?

Thanks for the trials, hope we can find the culprit(s).

It was 100ml 5% vinegar. Didnt wash the zinc with water after as in the VDS paper though, so was pure vinegar at the basing stage.

The goo did stick to the spoon, a bit like pine resin. When dried though, it became hard and brittle and could be ground to powder

Ok that is 13mg/ml and should not goo like that. Your concentration was spot on perfect.

From here I can't stop thinking about the carbonates that were used for obtaining the harmaline.
In one occasion I wanted to use sodium carbonate as a base to in-situ crystallize on the microscope glass, and I got a goo-ish effect on the glass. I have used only ammonia since, for that purpose.
Do you think it is possible that there were carbonates in the harmaline, remainders? This could be most likely the case if you just dropped dry base-ing powder in the liquid to obtain the harmaline. Was it like that?

Good point Jees. I actually used a sodium carbonate solution for the separation, not dry powder, but didnt wash the harmaline much after precipitation so there probably was some carbonate contamination. The separation process took so long, I got impatient. Next time Ill stick to ammonia all the way through and get a meter to measure the pH depressions. Sounds easier.

You have been haunted by that goo spook enough by now, time for a change in tactics and see if that helps

By the way, after I precipitated THH with ammonia I was a bit insecure that some THH could still escape this process, so I ended with lye to take it all a notch higher pH. Washing takes care of the lye traces.

I can't explain your low yields either. But I do second Jees that carbonates might be the culprits. In an attempt to get rid of the phenomenon, I Mansked my combined harmala's again. In that batch and by using ammonia only, no more goo-spook was encountered. I find the Manske, or whatever you would call this ion-exchange precipitation reaction, to be a very elegant and very beautiful reaction and never bother too much about doing one more. I do my Manskes with an equal volume of concentrated rocksalt-solution and make both reagents hot before combining. Then I let the recipient slowly cool and come peeping every few hours to check on the progress . If you have some more material, you could check for yourself of this does the trick or doesn't, let us know

Would there also be an easy direct way, to pull just the FBs without the sodiumcarbonate, e.g. with Naptha?
Or to wash out the sodiumcarbonate somehow easily?

Carbonates can just be washed out using water, or a dilute ammonia solution, as freebase harmalas are not very water soluble. I just didnt take the time to do this as was in a hurry to finish the separation.

Do we know how much the FB Harmalas are water soluble? I read a lot here and there, and am therefore a bit hesitant about water filtering them, as I don't know how much would be wasted...
Ammonia is a bit more problematic to get here, than the US, and unfortunately stinks terribly...

Check out the dmt nexus wiki. Chemical properties of harmalas and other relevant alkaloids are listed, solubility, melting points etc. A small amount of sodium carbonate can be used to make water slightly basic. This would still pick up any excess sodium cabonate mixed in with your harmalas. Ive washed harmala freebases many times with negligible losses.

The problem is a bit the Wiki also just says "Low solubility in distilled water" for Harmine and "Slightly soluble in basic water, poorly soluble in distilled water" for Harmaline. These are all a bit vague terms, and I honestly have no idea how much "low,slightly and poor solubility" would be in proper numbers.
But I guess I will just wash it with dilute sodium carbonate solution 0.5% like mentioned in the paper as a possibility.

Edit:
I also think the "Insoluble in salt-saturated water" for the HCLs in the Wiki isn't really correct. As already some GC/MS has shown there is still some in the salt water and also in the book from 1847 it is said that a "tolerable" amount remains in the salt water. No idea how much that is in reality...

Dear friends, thanks to Endlessness , we finally have some analytical LC/MS results of some of the samples in this thread . I tend to be a little disappointed in the purity of most of the samples, but on the bright side, the results give some strong indications about what techniques to follow. I’ll list the results, will elaborate on the preparation of the samples and will try to give some conclusions as well. In general one could say: stick to the VDS-protocols, stir like crazy (or use something that will do this for you) and go slow during basification…

1)Harmine sample prepared following VDS’s-extraction protocol with 4 ‘Manskes’ instead of five, followed by pH specific separation ending in fast rising slope of the precipitation-curve (so in fact following VDS’s experiment 2.3).

Result: 78% harmine, 4% DHH

Endlessness guesses the remaining percentages were moisture (indeed, I did not dry any of the samples by heating or applying dessicant and they were not sent absolutely airtight neither ), or remaining salts. He states that these are not alkaloids. I think salts are not probable either, because I used ammonia-washes to clean up the alkaloids. These should have washed away any remaining salts. So moisture might be suspect number one. Anyway, this means there is a DHH-contamination of less than 5% (4/82) in the isolated harmine. Not that bad. I also have to add that I used this separation method in a rather quick fashion. Possibly, by letting the solution stand for a while under constant stirring, an even better result might be attained by letting the solution reach equilibrium and provide more precise pH-measurement.

2)Harmine isolated by bicarbonate-separation following VDS-experiment 2.4 (post #160)

Result: 68% harmine, 6% DHH

This gives a DHH-contamination rate of 8%. As explained in a later post, the influence of carbonic acid wasn’t known then. This might have led to a larger contamination rate. Anyway, as we came to realize, CONSTANT STIRRING OF THE SOLUTION can prevent this problem by decomposing the carbonic acid.


3)Harmine from HAR-DHH to HAR-THH conversion (post #169): clean-up with Na2CO3 as base after additional Manske

Result: 63% harmine, 10% DHH

This gives a DHH-contamination rate of 14%, which is pretty bad. But, interestingly, I reread my post (page 9, post #169) to find out that here again, the presence of carbonic acid messed thing up. Another confirmation of THE IMPORTANCE OF CONSTANT STIRRING when working with (bi)carbonates! It is disappointing that this was the cleanest harmine I ever observed mAcroscopically. I still find it difficult to believe that something looking as pure as in picture 20 of post #169 would have such a high contamination rate….or is the slow basification process that really cleans up the alkaloids?

4)Harmine from HAR-DHH to HAR-THH conversion (post #169): clean-up with NH4OH as base

Result: 49% harmine, 9% DHH, 4% THH

Even worse than sample 3. Same crude contaminated harmine. It seems that the extra Manske of sample 3 removed the THH that was present in this sample.

5)DHH isolated by bicarbonate-separation following VDS-experiment 2.4 (post #160)

This sample was sent in the first batch and got lost. I did not have any left the second time.

6)DHH from #5 after removal of first-precipitating fraction

Result: harmine 8%, DHH 74%

So a harmine contamination of almost 8%. This is a bit better than the result of the corresponding harmine fraction in sample 2, but this sample was selectively purified by deliberately discarding the first small fraction to precipitate when rebasifying sample 5.

7)THH from last higher-yield DHH-conversion (post #177)

Result: 4% harmine, 5% DHH, 91% THH

Now this is interesting. The percentages all add up to 100! Another interesting thing is that this reaction was done with DHH from a pH-metric separation. I did not have any of this left to send for analysis, so indirectly we can gather some information about it. When comparing the 4% of harmine in this sample with the 4-5% of DHH in sample 1, one might conclude that pH-metric separation worked equally well in both directions. However, we can not be sure about this. Anyway, of the DHH present in the reagent, almost 95% seemed to have been converted to THH (assuming we precipitated all of it and the remaining DHH as well). The key elements in this reaction were CONSTANT STIRRING DURING REDUCTION AND SLOW BASIFICATION. As we will see from the following samples, this really makes a big difference in yield and purity. Also, in this route, only ammonia was used throughout all reactions, basifications and washings.

8 )THH Activated charcoal clean-up (post #159)

Result: 6% harmine, 20% DHH, 70% THH

Same DHH used as in sample 7. Only without regular stirring during reduction and basification

9)THH from HAR-DHH to HAR-THH conversion (post #169): Na2CO3 as precipitation base

Result: 10% harmine, 26% DHH, 28% THH

Wow, this is bad! A bad reduction as well as a bad yield as well as a large amount of contamination. And again, in this case the solution was not stirred during reduction. As well, the sodium carbonate and ammonia were dumped in after reduction. Here as well, no stirring was applied while working with bicarbonate.

10)THH from HAR-DHH to HAR-THH conversion (post #169): NH4OH as precipitation base

Result: 8% harmine, 35% DHH, 50% THH

This is interesting. For this sample, the exact half of the same filtrate as sample 9 was basified, this time with ammonia. This was dumped in as well. As we see, even after correction of the missing percentages, the relative concentrations of the alkaloids are notably different, while the total yields were more or less the same (44 vs 47% respectively). This might indicate that the nature of the base does play a role in the final precipitation step.


So in conclusion: the LC/MS results show that the samples contain a variable amount of non alkaloid-mass. Hopefully, this fraction would mainly consist of moisture. Anyway, pH-metric separation of harmine and DHH following experiment 2.3 (protocol 2.1), was shown to yield an acceptable 95% separation of DHH from harmine. Indirectly deduced, a comparable contamination of harmine in the DHH fraction was observed as well. Also, the zinc-acetic acid reduction of DHH to THH (experiment 2.5, protocol 3), was shown to be very efficient at 95% conversion. All reactions and separations using (bi)carbonate yielded poor results, presumably because of the presence of undecomposed carbonic acid. FOR THIS REASON, AS WELL AS FOR REASONS CONCERNING CONVERSION YIELD AND PURITY, ALL REACTIONS MUST BE CARRIED OUT UNDER CONTINUOUS STIRRING.

One can not go wrong by following VDS’s protocols, but to make it easier for some people to follow, it might be helpful to write a tek, where the experimental methods of VDS are combined with the practical knowledge gained through our collaborative research. Therefore, I invite all Nexians to add their wisdom to this thread in the following weeks. I will then compile this knowledge into a practical tek. Jees, I think you play(ed) a major role in this research and would not want to finish this work without your approval. Oh, did I say ‘finish’? True, there are still some loose threads that need more research, but I think we have enough material now to help our fellow psychonauts gain access to pure substances, namely harmine, DHH and THH. Specifically, only ammonia-only routes can at this moment be confirmed. It would be very helpful to perform reductions and separations using the (bi)carbonates under continuous stirring and having the reactants analysed as well. But that's for some other time...candidates ?

Glad results are in da house, can't comment yet, now time to study them and going trough their relevant posts again. Thanks for posting An1cca and thanks to Endlessness

What interests me mostly now is how teks with ammonia compare to those with the carbonates, I admit to have a biased preference for ammonia in the workflow. Ammonia stinks: all it needs is working under the kitchen fume hood, or an open doors well ventilated room and this only involves the hand operated reactions which is limited time in the end.
It is so general obtainable in any store here, next to any bottle of bleach here is a bottle of ammonia. I was surprised to read here that someone cannot easily obtain ammonia. For those people, a carbonates route could be the solution.

An1cca what's your idea about choosing for carbonates vs ammonia? Leaning against the carbonates side?

Hey good to hear youve got the results back an1cca. Just had a quick skim through. Will take the time to go through them in detail later. Interesting how the reductions from mixed alkaloids came out with the worst yields and purity. This confirms my experiences bio-assaying the results of harmine/harmaline reductions versus those starting with fairly pure harmaline. The latter had a very distinctive effect which I reckon must be the thh.

I certainly prefer to use ammonia for all steps (separation, basification, washing). The more so after the results of the LC/MS. However, I think the (bi)carbonate route is worthy of investigation for those people who do not have access to a pH-meter. And I still think it is possible to get good results with them, if some precautions are followed...

In the meantime, many more questions have come up on which I will elaborate shortly (influence of duration of reduction, microscopic validity and correlation with purity, HAR-DHH to HAR-THH conversion can't go right with only one bicarbonate-step, decomposition of the alkaloids/samples,...)

Some answers, more questions ...

please, for the dumbest of us, say. me, when you write a tek, explain, what concentrations and ratios are best. bought a bottle of ammonia from the hardware store down the street just for the purposes of this thread, hope it is a suiyable product.

Of course we will ....

In fact, regular 'household concentrations' will do fine and just need to be diluted sometimes. If you can't wait, just read the method-section of VDS's article, he mentions the concentrations used for the different steps: https://doi.org/10.5281/zenodo.154442. For most experiments, 2% ammonia is all it takes (and it doesn't stink when kept in a syringe). Sometimes, you want strong ammonia for basification without too much dilution, then 12% is better suited. I've had 24% for a while, but got tired of suffocating every time I opened the bottle .

Now, some people might wonder if it's a good idea to swallow stuff that got treated with a bottle like the one you bought. If one wants to be sure that no other additives will be left in the product, here's a simple procedure to follow: put a known amount of ammonia with known concentration in a flat tray, take another tray and put the same amount of distilled water in it. Put both trays together in a box that can be shut airtight. Let this setup stand for 2 weeks. Now you will have two solutions with half the concentration of the original ammonia. Use the one made from the distilled water for your experiments...

Okay, some more answers and questions…
Time of reduction seems not to be correlated with efficiency. Sample 7: 9 hours; sample 8: 9,5 hours; samples 9,10: 22 hours. So again, this indicates the importance of stirring during the reaction. As well, it indicates that 9 hours of reducing under stirring are enough.
Moisture content as the culprit of the ‘lost percentages’? Unfortunately not so: after 30 min of drying in an oven on 100°C, the mass of sample 1 dropped by only 2%. Then what is the other stuff?
Can decomposition be an explanation for the results? All samples were kept in the freezer until they were sent. What happened next I cannot say. But harmine for example was shown to be stable for decades at room temperature. THH on the other hand? Perhaps part of the THH got oxidised to DHH?
Unfortunately, it seems that microscopical ‘cleanness’ (let alone macroscopical) doesn’t give any guarantee about purity. It can serve to identify the specific alkaloids however. I will put sample 9 under the microscope again to observe how ‘not-THH’ it looks…
And then for a theoretical question: if it is not possible to separate harmine from DHH with bicarbonate in one step (it needs 5), then how can we expect to obtain uncontaminated harmine after HAR-DHH to HAR-THH reduction by only applying 1 bicarbonate precipitation? It seems to me that this precipitate should be redissolved and reprecipitated with bicarbonate at least one more time to allow for purification. I think VDS might have overlooked this. In fact, I wonder what he would have written if he had access to LC/MS? We on the other hand never bothered to do melting point determinations. Perhaps his melting points carry the same amount of uncertainty than our microscopy? It’s so good to have access to Endlessness’ results, thanks again !
Speaking of which, what is the variability and measuring error of the LC/MS tests done? I have zero experience with this technique. Is it always as exact as we want it to be? It would be a shame to put our time in discussing results that in the end appear to be artifacts…

Cool to mention the make-your-own ammonia

In general I agree with your sentiments, with a reservation for further discussion on some points.


This I saw also immediately but I've always thought maybe it wasn't that much of carelessness? Actually because of that I started to accept that THH crashes out at higher pH values than DHH. The pKa values of THH on the net are very ambiguous, besides: pH depressions bring their own mechanics on the bench, so comparing pKa's is not helping much I think. But you have a strong point An1cca to not take things for granted that VDS has it all figured out.

Then on the other hand we've found him to be silent about other things too, things he must have known, we presume. Like the existing of the zinc salts at all, or how he dealed with the brown goo spook and how he nicely surfed around that. No coincidence right? So maybe he did knew for sure that only DHH and not THH could fall out under sodBicarb?
Maybe we should ask him?

Results are going to be better imho the more one gets the hang of it, these results here now are truly preliminary snapped. It would be nice if we later could have an evolutionary comparison.

This so far..

I would think so, but even he should have known that conversion of DHH can never be 100% so inevitably a part of the unreacted DHH will end up in the bicarbonate precipitate...

Not a bad idea to contact him and let him know the result of the LC/MS. Will make him think twice before stating that others are 'wrong' in their techniques ...