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Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols Options
 
Jees
#41 Posted : 10/22/2016 12:14:11 PM

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Nice,

I suspect that if you hit that nice yellow liquid with lye to 12 (is what I usually do), you get another dropping outs and you have an almost water transparant liquid left. I always thought that would be harmaline also. Unless it is another alkaloid that survived the manske? If it is harmaline then the good ole pKa approach is still valid to recover every single bit. After the depression stops, I suppose some still is to come. All my A/B steps end at 12 and always have good yields, like last time 6.8% rueHCL good for 5.8% FB.

I think I'm ready to do some work on the alks for making THH. Probably skipping the whole harmine-harmaline separation step, to end up with a mix of harmaline + THH. Simplicity rules
Twisted Evil

Love to have you here An1cca Pleased
 

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DreaMTripper
#42 Posted : 10/22/2016 2:33:54 PM

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A possible explanation as to why the pH drops when you first add ammonia is that its concentration is so low that it donates H+ (hydronium ions) to the water and thus the pH drops however as more is added the equilibrium shifts and the water then starts donating H+ to form NH4 and thus the pH rises as the concentration of H+ decreases and OH- increases.
 
An1cca
#43 Posted : 10/22/2016 2:58:07 PM

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Thanks DreaMTripper, and how do the alkaloids fit in? Because actually the pH first rises to above 7 before going down together with alkaloid precipitation. It seems that the alkaloids require some 'activation energy' in the form of pH-differential before precipitation starts... Confused
 
Jees
#44 Posted : 10/22/2016 11:23:05 PM

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Success Big grin

had it reacting for some hours (only) but also few times in the microwave, then it's getting on step big time.

So clean and free of the typical harmaline stamp.
I love the harmaline vibe though but it's great to have another tool.
No separation step done, not needed for traveling.

Grateful Love
 
DreaMTripper
#45 Posted : 10/23/2016 1:01:36 AM

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An1cca wrote:
Thanks DreaMTripper, and how do the alkaloids fit in? Because actually the pH first rises to above 7 before going down together with alkaloid precipitation. It seems that the alkaloids require some 'activation energy' in the form of pH-differential before precipitation starts... Confused

Oh yeah just read it again, well that's a good question and maybe beyond my basic knowledge! Some complex interactions going on there I think. Interesting stuff.
 
exquisitus
#46 Posted : 10/23/2016 1:49:41 AM
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can somebody please summarize and streamline the final results reached here in this thread, for those of us that find chemistry hard? thanx
 
Intezam
#47 Posted : 10/23/2016 9:29:33 AM

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^^
This (the full separation...etc) and the simplified caapi copy tek ?
 
Jees
#48 Posted : 10/23/2016 12:45:20 PM

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bird_people wrote:
...simplified caapi copy tek ?...
Cute term there but expect a wash of aya elite-ish objections Laughing

I think there is a need for cleaning up the OP paper wisdom, and we might get to one eventually and put it in the wiki. There's one already but for dmt n-oxide, fairly same yet pulling dmt with a non polar solvent eliminates all ZnOH issues automatically regardless of the base used. Since we don't pull harmalas this way, a nuance might be in order, one dedicated for harmalas.

VDS has 2 short protocols for making the THH on page 37
PROTOCOL3 wrote:
...filter off unreacted zinc and add base (ammonia or sodium carbonate solution) until no more precipitation is observed...

PROTOCOL4 wrote:
...Filter, discard unreacted zinc and add an excess of NaHCO3 to the mother liquor, thereby precipitating the harmine-fraction, filter
|
add excess base to filtrate to precipitate the THH-fraction, filter and discard filtrate...

He nowhere points out that it is only ammonia that keeps us free of solid ZnOH. For a moment he keeps so silent about it I wonder why. And recommending sodium carbonate is a ticket for getting ZnOH in your end product for sure.
The notion "excess base" can hardly point to a bulkload of lye (as I've found out to work), this from the viewpoint of harm reduction about which he is fancy over + care for THH concerns. Again not specifying which base to use suggests that it doesn't matter, which it does according to our findings.

Maybe he sees no issue in consuming ZnOH? The MSDS sheets that I found (so far) could not confirm anything in this matter, input is welcome. The Zinc food additives on my shelf are zinc-gluconate (22.5 mg/tab) and zinc-citrate salt (25 mg/tab). Since I was able to obtain 335 mg ZnOH of one reaction, this doesn't looks safe to neglect, if consumable at all. If it would not make one sick then a firm diareaaaaahgh is in line of expectations.
Anyway the formed ZnOH would skew his recovery numbers and render claims about it trustful.

Confused
 
Jees
#49 Posted : 10/23/2016 1:11:41 PM

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Another critical note:

Page.29 wrote:
...Just as with the pH-metric method of separation, these results have important implications for harm-reduction. Because when only one separation cycle is done, a substantial amount of DHH is contained in the presumed harmine-fraction...


Page.28 wrote:
...On popular websites describing the separation of Syrian rue alkaloids, it is postulated that harmine can be separated from DHH on the basis of their different pKa, claiming that at a pH of 8,75, 92% of the harmine present and only 8% of DHH present will precipitate [Dmt-nexus 2016a, Erowid 2016a, Shroomery 2016, Mycotopia 2016]. The above experiment clearly contradicts this statement, showing that at pH 8,50 all of the DHH has already precipitated. This has important implications for harm-reduction, as DHH is a much stronger MAO-inhibitor than harmine [Herraiz et al., 2010]...
When it comes to separating he might have a valid point, we are called out to confirm his claims I guess.

But harmaline is dangerous?
Because it is a better maoi?
I was lucky and not died along the way Pleased

A document I found about Herraiz 2010 is
"Food and Chemical Toxicology"; beta-Carboline alkaloids in Peganum harmala and inhibition of human monoamine oxidase (MAO); Herraiz T, González D, Ancín-Azpilicueta C, Arán VJ, Guillén H; December 2009
which indeed covers the issue, but I fail to read the danger what VDS is implying, harmaline being just a tad better maoi than harmine, see attachment. Or is the scale of that graph visually misleading (logarithmic)? Are there other sources about the maoi potency differences between harmine and harmaline, all help welcome. Yet I feel the expressions used by VDS are competed by practical experiences (being these subjective though). The body load is heavier with harmaline yes, but coupling this to maoi-power is not the same I think.
 
pitubo
#50 Posted : 10/23/2016 2:03:18 PM

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I wouldn't worry too much about the dangers of zinc ingestion. If wikipedia has it right, 150 milligrams is mostly harmless.

What I do worry about is the possible co-contamination with lead, cadmium and arsenic. These heavy metals are not only very toxic, but also cumulatively toxic. Excess hydroxide or ammonia will not wash their salts out of precipitated freebase harmalas.

In this light, the harm reduction claims of the paper become rather questionable, because it encourages people to experiment with zinc powders, while no mention is given about the potential dangers of using impure zinc powder.

I have yet to study the paper exhaustively, because I found the writing style a bit intractable. I have made a printout that will better allow me to draw a flowchart of the successive reactions and a list of resulting fractions.

Despite my complaints about the lack of warnings about the dangers of using impure zinc powder and the absence of more thorough analysis of the results, I am happy that the paper was written and published. It is yet another rich data point and has proven a new stimulus for follow-up experimentation.
 
pitubo
#51 Posted : 10/23/2016 2:08:29 PM

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BTW, AFAIK when carbonate ions are added to a solution of zinc ions, zinc carbonate forms and precipitates, not zinc hydroxide. Whereas the latter can be redissolved with excess hydroxide or ammonia, the carbonates cannot.

Another idea that sprung to mind: on page 8 of the paper recrystallization from 96% ethanol is mentioned, perhaps this could also be used to separate zinc hydroxide or carbonate from the harmala bases.
 
DreaMTripper
#52 Posted : 10/23/2016 3:36:55 PM

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Agreed, definitely cant use NaCO3 (sodium carbonate) it will precipitate ZnCO3 with your alkaloids an excess of NaOH or NH3/Aqueous NH4 should be used. Some complex interactions going on as explained here..
"...In the presence of excess NH3, Zn(OH)2 dissolves forming a tetra-amine complex. At low pH, there is the possible formation of a double salt"
To avoid any contamination from toxic contaminants that are in the Zinc you could use Zinc citrate (just read Jees is all over that nice one)
"Zinc citrate is approximately 34% zinc by weight" Looks cheap and easy to get.(Same applies for DMT-n-oxide reduction).
Yeah Jees although commonly used Zn(OH)2 is not going to be pleasant however it is ingested.
I think I would be inclined to wash the collected THH with pure cold water rather than dilute base I doubt much would be lost.
 
pitubo
#53 Posted : 10/23/2016 3:49:12 PM

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DreaMTripper wrote:
To avoid any contamination from toxic contaminants that are in the Zinc you could use Zinc citrate (just read Jees is all over that nice one)
"Zinc citrate is approximately 34% zinc by weight" Looks cheap and easy to get.(Same applies for DMT-n-oxide reduction).

You must use metallic zinc. Zinc salt are of no use in the reduction reaction, because the zinc is already in an oxidized state in these salts. Only metallic zinc has reducing abilities.
 
Jees
#54 Posted : 10/23/2016 5:38:38 PM

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Thanks pitubo for mentioning the zinc purity, lab rats think easily in terms of lab grade, while the more mortal world out there is vulnerable for whatever the internet sells. This one should be in a very big hard text style warning.

The one time I used citric acid was an attempt to re-dissolve my already dry and hard ZnOH, I could have used another acid but that was just in hand reach. Once dissolved from there I could do some base experiments. So the zinc citrate I had was not to perform an actual reduction with, but simulating the phase after a reduction and after taking the metal zinc out. Play with the basing was the song then, thinking it did not really matter which kind of zinc salt I ended with before the basing starts.

And yeah right sodium carbonate leads to zinc carbonate, not zinc hydroxide Thumbs up
I knew that but I had a brain fart going there Embarrased

Thanks for the adds guys.
 
DreaMTripper
#55 Posted : 10/24/2016 3:15:39 AM

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pitubo wrote:
DreaMTripper wrote:
To avoid any contamination from toxic contaminants that are in the Zinc you could use Zinc citrate (just read Jees is all over that nice one)
"Zinc citrate is approximately 34% zinc by weight" Looks cheap and easy to get.(Same applies for DMT-n-oxide reduction).

You must use metallic zinc. Zinc salt are of no use in the reduction reaction, because the zinc is already in an oxidized state in these salts. Only metallic zinc has reducing abilities.


I was thinking that if you raise the pH the Zinc will separate from the citrate leaving unbound Zn available for the reduction. However I cant find the pKa of Zinc citrate anywhere. Its soluble in dilute acidic solutions however it's unclear whether that would leave insufficient Zn left if Zinc citrate starts to precipitate. It would require very careful adjustment of pH to just below the pka of harmine so not to cause precipitation but again that could produce Zn(OH)2 in which case there is another problem with the solubility. Actually, if it is done added after harmine has been separated then you have a greater range to play with. The pH maybe could be raised to 8.5.
If you can get high grade Zinc then it would save a lot of hassle however cadmium is known to be found with Zinc often and may even be present in food grade products.
 
An1cca
#56 Posted : 10/24/2016 8:13:28 AM

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An1cca wrote:


Jees wrote:
I'd like to change to this question: is it possible to precipitate all ZnOH with sodium bicarbonate? Have the solids filtered out, then base the filtrate further (with sodium carbonate or lye but sure no ammonia) to see if any more ZnOH goes solid.
This experiment could pave the way to the ammonia-free route you were telling about.


Good thinking, gonna check this out...



So this is what I did:

Added 3g of Zn to 100ml of acetic acid 7%, let it react for 24h. Filtered off Zn (starting pic1).

Added sodium bicarbonate solution (8g/100ml) and later on just sodium bicarbonate powder (making sure it is all dissolved before adding more). Nearing pH 6, clouding appears (pic2). However, unlike with sodium carbonate, the precipitate causes clouding like ammonia, no flocculent precipitate. Further addition of sodium bicarbonate increased the clouding some more, and now some floating particles could be observed. At pH 7,5, I decided to filter. In contrast to the sodium carbonate precipitation, the solution was easily filtered and the filtrate was absolutely clear (pic3-5).

Then I added a lot of sodium carbonate carbonate to the filtrate that raised the pH all the way to 9,83. This time, NO MORE PRECIPITATION was observed.

So, these results are in line with VDS's protocol 4, where the harmine fraction coprecipitates with the zinc carbonate. In fact, this can be seen in his results, where the weight of this first fraction is about double of the expected harmine-yield. The above experiment confirms that the THH fraction can consecutively be precipitated by sodium carbonate as well as with ammonia.

However, the harmine fraction can not be redissolved in acid and reprecipitated with sodium carbonate without getting the zinc carbonate fraction as well. In this case, ammonia SHOULD be used (or a manske as he did as well). So this is an ERRATUM in protocol 4.

The conclusion is that an ammonia-free route to THH synthesis IS possible by first precipitating the Zinc-ions as carbonate with sodium BIcarbonate, filtering them off and then precipitating the THH out of solution with sodium carbonate. That is, if THH is not precipitated by sodium carbonate (as is indeed suggested by the experiments of VDS). I plan on testing this hypothesis shortly by using harmaline obtained from the pH-selective precipitation mentioned above.

I also have some numbers on this. I reacted 6,008g of mixed harmine-harmaline and after doing the separation as mentioned earlier, obtained: 2129mg harmine fraction, 273mg mixed fraction and 3064mg harmaline fraction. I might get a hold on a (very) basic microscope this week, then I can try to identify the alkaloids...

It seems our collaborative research is refining the paper's protocols into some definite and detailed 'VDS-Nexus' protocols! Once we have the info, I will try to edit my OP and write a summary (as suggested by exquisitus).
An1cca attached the following image(s):
pic1 at the start, zinc filtered off.jpg (56kb) downloaded 250 time(s).
pic2 Clouding appears nearing pH 6.jpg (43kb) downloaded 251 time(s).
pic3 Clouding increases no further.jpg (40kb) downloaded 248 time(s).
pic4 Filtrate perfectly clear.jpg (57kb) downloaded 247 time(s).
pic5 residue easily filtered off.jpg (28kb) downloaded 246 time(s).
pic6 Excess sodium carbonate does not provoke precipiation.jpg (58kb) downloaded 247 time(s).
 
ijahdan
#57 Posted : 10/24/2016 10:23:50 AM

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So, starting with a mix of harmaline and harmine, after the zinc reduction and filtering excess zinc, one could add sodium bicarbonate to precipitate zinc carbonate (and any remaining unreduced harmaline). After filtering this, the pH could be raised more using sodium carbonate (or ammonia) to precipitate a mixture of thh and harmine?

Also, this cadmium issue is concerning. Is there any way of obtaining 100percent pure zinc?
 
An1cca
#58 Posted : 10/24/2016 11:17:35 AM

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Ijahdan, after the reduction and filtering of excess zinc, use sodium bicarbonate to precipitate all of the harmine and all of the zinc ions present as the carbonate salt.

Clean up this fraction by redissolving in vinegar and reprecipitating the harmine with ammonia. The zinc ions will stay in solution.

To the filtrate of the first paragraph, add ammonia or sodium carbonate to precipitate THH. Check protocol 4 at the end of VDS's paper but do not use sodium carbonate as the reprecipitating base for harmine.
 
Jees
#59 Posted : 10/24/2016 11:28:30 AM

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An1cca wrote:
...The conclusion is that an ammonia-free route to THH synthesis IS possible by first precipitating the Zinc-ions as carbonate with sodium BIcarbonate, filtering them off and then precipitating the THH out of solution with sodium carbonate. That is, if THH is not precipitated by sodium carbonate (as is indeed suggested by the experiments of VDS)...


The underlined should be sodium BIcarbonate I presume. I had myself edited so often, these words mingle up so easily LOL.
Good thinking & tinkering by the way Love
VDS suggested that sodium BIcarbonate would not precipitate THH but would precipitate harmaline (this was his criticism on the "popular internetsites" ). The 'distance' between harmine-THH should be bigger than harmine-harmaline, this is indeed also reflected by Nitegazer's TLC's.

So your efforts indicate there's a full ammonia free route if we first separate harmaline from harmine. Set harmine aside, reduce the harmaline. Precipitate the ZnOH or ZnCO3 and filter off. Then precipitate the THH. So actually 2 separation steps necessary. Yet separating harmine-harmaline in advance needs tact according to VDS paper.
Or..
Have the harmine+ZnOH (or harmine+ZnCO3) precipitated together and separate those later a la manske. [**]
What I also would like to do is to see how a full precipitation of ZnOH or ZnCO3 (not dry but still in suspension) behaves when ammonia gets pored on. I did those experiments on a smaller scale (1 ml ammonia was enough) successfully but would like to do it in real-scale. If this works as well as a complete ammonia-only basing, it could reduce the use of the amount ammonia substantially.
[**] If this works great then a manske could be replaced with just adding some ammonia (amount to be established) to the harmine+ZnCO3 mixture and filter. Not ammonia free but close. Has to be checked.

* * *

If people want to make use of the harmala "depressions" as a separation indicator, I would suggest a pH meter with 0.01 resolution. Forget pH strips to make any separation. And also not to work with too strong a base (as is my 8mol/L) because I've found to very easily overshoot a depression, making it myself more difficult.
The neat thing about those depressions is that the calibration at absolute values becomes less important and the shape-behavior of the curve chimes in as a give away. Yet one can not go around this ghetto style, some more fingerspitzengefühl is welcome.

* * *

To come to a "guide" or tek, I think we could make a distinct in 2 ways:

1) a route of strict minimal fuzz, the fast way, no separation steps, reducing harmine+DHH into harmaline+THH, base with ammonia only, filter & wash. It even allows for having no pH checking at all if one just uses enough dirt cheap ammonia, wash well afterwards. One just doesn't know the harmine/THH ratio but this is for when you don't care. I had a blast of a pharma session with it.

2) for those who want harmine and THH separately: including the several separation steps, likely better pH metering, more fingerspitzengefühl, more time consuming ...


 
Jees
#60 Posted : 10/24/2016 11:32:28 AM

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Quote:
Clean up this fraction by redissolving in vinegar and reprecipitating the harmine with ammonia. The zinc ions will stay in solution.
Yes this is what i was referring at when doing no manske Thumbs up
I've been using too much words Pleased
 
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