Many people claim that they know what pure harmine and pure harmaline feel like. This is often used to claim that they therefore know what pure THH feels like. I want to point out that this is probably not true and that the vast majority of the time many SWIY's are simply eating mixtures with different ratios of harmine/harmaline (at least when using extracts from peganum harmala).

Using the NaCl + sodium carbonate precipitation method many try to take advantage of the pka difference between harmine and harmine to separate the 2. This separation is incomplete.

I post two example GC analysis. The first is the initial precipitation (pH ~ 8.5) which led to a brown powder. The second is a more basic precipitation (pH ~10) which led to a yellow powder.

Note that the first precipitant is contaminated with harmine and the second is a mixture of harmaline and harmine. Now this of course will vary between the source plant material and the individuals technique. But the point is that this separation is incomplete. It should be expected that its incomplete pka precipitation is not a fool proof method of getting pure compounds. Acquiring pure compounds from plants is very difficult and often requires chromatography. Mimosa happens to be a nice exception fortunately for those who like dmt. Most other plants and compounds are not that easy to get pure.

So all this debate about placebo effects and knowing what these pure alkaloids feel like is largely pointless when most people really don't know what ratio of what alkaloids they are ingesting.

It would be very interesting to see a GC of a plain Caapi solution that has been raised to 7 to see if the THH pKa figure of 6.9 is accurate. The Harmine sig of 212 would stand out against the THH and we can see if taking advantage of the different pKa's would indeed be an effective sep method, at least for kitchen work.

again, thank you for taking the the time & resources to post these results

Just out of curiosity where did this theoretical number come from?

This is quite interesting. I always figured that harmaline was yellow and harmine was white. I've always taken it as a given that the PKa seperation was incomplete but the two seperate precipitates contained mostly harmine at 8.5 and mostly harmaline at the higher pH which accounted for its colour.

What's this yellow discolouration all about then?

There are many things that cause colors to be weird. From minor impurities to the way the molecules arrange themselves when they are released from a solvent. To how the crystals are formed. Even in solution I've seen 99.9% pure compounds change the color of a solution from a temperature change yet no degradation had happened (on a totally different kind of compound not alkaloid).

How was pka determined? There are many ways of doing it.

Thanks for the useful and interesting tests, burnt.

If THH precips around ph7, doesnt that mean it is hardly soluble in distilled water? seems like a pretty easy way to see if you have pure THH.

If its a salt it will dissolve easily. As base neither harmine, harmaline, nor THH dissolve well in water. At least at room temperature.

Interesting... I've updated the wiki page on solubilities a little to say that the freebase harmalas are "poorly soluble in distilled water." Would you say this is accurate, burnt? you know better than me. There is a little bit of editorial about separating harmalas by ph precip you might want to edit. I also updated the ibogaine solubilities in acetone. I think this page needs a little attention...

https://wiki.dmt-nexus.m..._and_Physical_Properties

According to Merck index they are slight soluble in water, alcohol, ether, and chloroform as bases. Stuff is tough to dissolve in general unless they are salts.

Help in that page would be greatly appreciated! Please cite sources whenever you can .

I've been putting in my 'to do' list to add info about vasicine, vasicinone and deoxyvasicine in the 'relevant non-psychedelic compounds' part. I started a discussion about them in this page.

Burnt, maybe you have something to comment on that thread? Do I remember correctly that you tested manske salt-precipitated harmalas to contain none of those alkaloids?

sorry to derail the thread... it all started when I noticed you had more correct info than the wiki page. I was going to update some of the info there with merck data, but then I realized this page is on the nexus already:

https://wiki.dmt-nexus.me/w/images/8/81/MERCK.pdf

which is in some ways a more complete version of that list. I think the merck data would be a good place to start and then update any bits that are proven wrong (it does happen) or unusual (like solubilities in limo).

anyways, the wiki page outlines a process of separating harmalas by ph that you disproved pretty well here...

^^Well the ratios will vary and I'm sure sometimes people end up with either more pure or less pure harmaline. The point is that its difficult if not impossible to get complete separation using such a method. The only way to really separate the 2 is chromatography.

burnt, thank you very much for this thread!

If we are to measure by the freebase calculator (which uses pKa calculations), then at pH 8.5, 86.32% of the Harmine will be precipitated, while only 4% of the harmaline will have done so. At pH 10, the rest of harmine will precipitate (another 13.2%, for 99.5% total). Also at pH 10, the other 61% of harmaline (so 65% total) will have precipitated.

Isnt that pretty accurate with your analysis? In the first there was only small amount of harmaline, in the second there was quite a significant amount of harmine still present (according to calculator, 13.2% of total original harmine content, which if originally was present in bigger ratio than harmaline, it would make sense that in the second precipitation there was nearly as much harmine as harmaline).

If the calculations are correct, this would also show that pH 10 you are still missing a big part of your harmaline (35% of it) which still havent precipitated.


So while I completely understand and agree with your point that you can never be perfectly sure about your separation, a product precipitated at pH 8.5 will be mostly harmine. The product precipitated with higher pH, though, will probably have significant harmine contamination, not be pure harmaline. How much contamination will depend on original ratio of harmine:harmaline, which one can simply not know beforehand. So even if after the first precipitation (ph 8.5) in your case, at pH 10 there is only 13% of original harmine, if there was 3 or 4 times as much harmine to begin with, then this 13% will be a very significant contamination, maybe more than half of the precipitation at pH 10.


But, this leads me to two thoughts: What about selectively separating through 3 different pHs? So lets say we make a first precipitation at pH 8.5 to have mostly harmine. Then make a precipitation at, lets say, pH 9.1. This middle precipitation will have another 10% of the harmine (for a total of 96.2% of total harmine content already precipitated in these first two precipitations). In this precipitation at pH 9.1, another 12% of original harmaline content will precipitate (for a total of 16.63 % of original content precipitated in these two precipitations). So this means you would have 3 products: 1 with basically only harmine, 1 with mix of harmine and harmaline, and one with mostly harmaline but some harmine contamination (amounts which depend on original ratio of harmine:harmaline in seeds).

Redissolving each of the batches and repeating process of selective pH precipitation could separate them even better.

Maybe this isnt a perfect solution but at least it lets people have a general feeling of how the separate harmalas feel in bioassays, knowing that there is some contamination. Its definitely no pure separation, indeed one would need chromatography or similar for that, but at least for the general purpouses used here I think its enough, dont you agree?

Another question I have, maybe you can test this with some pH meter, burnt: In a harmala solution, whats the maximum pH that sodium bicarb can raise the solution to? I've gotten so many contradicting answers about this and nobody ever really tested in this specific case, which I guess is different than testing the pH sodium bicarb can take pure water to....


And ouro, I will edit the wiki page to put a warning regarding the separation not being perfectly pure, and link to this discussion here, thanks for the heads up!

Well SWIM imagines that if one does multiple harmine precipitations in the pH 8.5 or so solution there will be less contamination in the higher pH precipitations. But the aqueous solution will probably always reach a point where harmine just doesn't precipitate because its no longer saturated and thus precipitation stops working even at higher pH's. The ratios and amounts SWIM has no clue about.

Your proposal may very well help endlessness but again SWIM imagines there will always be a point where the solution is not so saturated and thus is always slightly ineffective. But remember SWIM is quite a stickler when it comes to purity so it depends how pure one is looking for.

As far as pH tests SWIM has no time at present. Maybe in future.

Hi guys,
Yes. It has been a long time...I still peek in to see if everyone is allright!
I really have to say that I missed the crux of the whole THH fiasco and seriously miss the product known as FV THH, whatEVER it was...

Even after all of the 'bio-assayer-bashing' I proudly claim to have clearly felt a difference between the various harmalas that were vended by FV. I used them hundreds of times and while I will not expect everyone to believe me I will expect those same people to know that they cannot tell me what I feel and do not feel. Not everyone can taste the difference between brands of bottled water, but I can. The people who cannot tell a difference think I'm nuts...Such is the world. Still it spins.
My point is this...whatever it was that was sold as THH, I LIKED IT...And now, because of exactophiles and mass spec charts and because a member of the Nexus was trying to service the community while maintaining a relationship with it and exhibiting what I can only assume to be an attempt at etiquette....Now that product is gone....and with it the method involved in obtaining it.
Now I see threads devoted to the struggle of finding this magical substance. I check back to see if any head-way has been made only find very little.

If I am missing the final HARMALINE/HARMINE REDUCTION TO THH recipe then forgive my rant and please point me in the direction of said recipe....I REALLLLLLLLY need some. Even if it the same thing as FV's THH...

Thanks..

Esp

Espiridon this may be a place to start, if you haven't already seen it: Harmaline to THH reduction with zinc and vinegar works! (GC-MS results)

^ I tried that a while back but the flavor of the product indicated that I didn't successfully separate excess zinc from the alkaloids, so I made myself puke just in case. I wish there was more solid information on THH and like, getting it.

seen lab tested non consumable standardized caapi extracts out there, composition 50/50.

...


Well, I guess it'll be Adam's catalyst, sodium borohydride and a pad of argon then. Expensive but reusable. Caapi is too expensive to used as frequently as I'd like, and with a bundle of unwanted harmaline....the choice seems clear. It'll be awhile before I amass the necessaries but it will happen. Thank the universe for Sasha Shulgin, may he rest in peace.


E

A little off topic, have experience with THH from back in the day, and over the years have learned that the combination of harmine and THH in equal ratios (for example 190mg harmine + 190mg THH) is an unbeatable combination. They work together in harmony for the best experience possible. Just my 2 cents. Isolated THH has nothing imho on the combination of the two in equal proportions.

This study by Callaway (see page 2 and page 3) shows this nature (with a little bit of help from woman or man) derived 1:1 ratio of harmine to THH is found quite often in advanced brewing by the UDV, Santo Daime and even Shuar Indians:

Callaway, James C. (June 2005). "Various alkaloid profiles in decoctions of Banisteriopsis caapi"
http://catbull.com/alamu...in%20aya%20decoction.pdf

In the chart on page 2, just multiply the 1.83 for harmine or THH or other example figures by 100 to get the actual mg amount in the brew.

See page 208 of "The Chemistry of Heterocyclic Compounds, Indole and Carbazole Systems"
By W. C. Sumpter, F. M. Miller":
https://books.google.com...hydroharmine&f=false
hxxps://books.google.com/books?id=2NH-cagtLSoC&pg=PA208&lpg=PA208&dq=hydrogenation+of+both+harmaline+and+harmine+gives+tetrahydroharmine&source=bl&ots=CTMkhD1z5B&sig=KfeGhd6bK0ZtPCiK99xBNnj2rKY&hl=en&sa=X&ei=5hKEVbrcLZKqogTKnqaoBw&ved=0CB4Q6AEwAA#v=onepage&q=hydrogenation%20of%20both%20harmaline%20and%20harmine%20gives%20tetrahydroharmine&f=false

A good dose of THH ranges from 150mg to 225mg and a good dose of harmine ranges from 150mg to 225mg. The two in combo is a perfect experience imho.