Godspeed on you

I was wondering what the smell was...







Hint: "God's pee'd on you"

Whatever does the job

Wonderful! Many thanks to you Loveall and good luck on your projects

The red color could come from other things, i have encountered it in 2 situation, working with mansked freebase harmalas, when i leave it in open air it turns red (much faster next to a heat source) and when i'm infusing harmalas into leaf using ethanol it turns red(maybe not all of it) but it was still quite active

One day when i'm better equipped i will coninue the harmalol hunt

Ok, time to test this out more.

This time will make a rue tea, filter, base, collect precipitate and keep the filtered base.

The filtered base should have Harmalol along with other stuff.

Then to the filtered base add salt in increments (say 2.5%). Stuff will crash out (as Sakkadelic showed in the first post). Then check if one of the fractions is a Na/Harmalol salt.

Attaching a paper that goes over the ionization of harmalol.

Key take away is that (surprisingly) the -OH group looses its proton first (pKa ~ 8.6), followed by the NH+ (pKa ~ 11.3). That is, sequence (a) in the image below (not sequence (b) ). They also mention that in the intermediate pH (~10) a stable quinone forms which is yellow (compounds 5b in image) and explains the unsually high pKa for NH+.

In practice this means that we want to be at a pH at least one unit above 11.3 to try to form the Na-Harmalol salt that may crash out because of the common ion effect with NaCl.

This could also open up a different way to clean up any possible harmalol (using pH instead of salt concentration), as proteins should not need such a high pH. Here is a proposal I plan on testing:

- Rue tea
- Basify to pH~12.5 and filter (reserve filtrate for the usual Harmine/Harmaline extraction).
- NaCl crash of basified filtered tea (13% as a first guess), filter "goop" and keep it.
- Extract goop with 13% NaCl solution at pH~9.8. Most proteins should remain insoluble, but harmalol may go into solution, possibly with a strong yellow color due to the stable quinone that forms at this pH.
- Infrease pH to 12.5, Na-harmalol salt of better purity could crash out of solution.

Ok, some partial results working on the 1st filtered basified water (pH~12.5) (this typically gets thrown away).

Added salt in 6% increments up to 30%. Stuff that looks like junk crashes out (as others have seen) at each salt addition except at 24%. Looks like junk, but not sure if Harmalol could be in what crashes out or not.

At 30% salt, moved to the pI of Harmalol (~9.8 I believe). More crashes out. Put the filtrate in he freezer but nothing much seemed to happen.

Then added acetone. Interestingly, some white stuff forms and settles to the bottom of the water (doesn't look like salt see image below, sometimes salt can crash out when adding acetone if near saturation depending on how the Gibbs triangle looks - someone wrote a thesis on this on the 1920s I believe). Because of the presence of salt, an acetone rich layer forms on top with a reddish color.

So now there is stuff crashing, stuff still in the water, and stuff in the acetone. Could the harmalol be in one of these layers?

Will separate the acetone and see if anything crashes when freezing. Will also freeze after adding a touch of HCl. May also evaporate. Ideas welcome. Cheers.

Interesting about the harmalol zwitterion. It makes sense that the OH proton goes first because of stabilization through the quinoid degeneracy.

Did you find a TLC spot for harmalol already? I guess that would help you I.D. if you could run TLC on each of the phases you've got there. Another possibility would be removing the methyl group from a sample of harmaline by some established procedure, if you have that capacity. Then you'd (with any luck) have a reference sample for harmalol.

I did more experiments with trying to get harmalol again.

This time used ethyl acetate.

Test was:

- 100g rue water extraction, settle/decant
- Base with NaOH, filter to catch Harmin/Harmaline
- Filtered water is not thrown away. It may contain harmalol.
- Acidify filtered water and filter again (new gunk forms)
- Make slightly alkaline. I got to 8.4. Maybe 9+ is better, IDK. Idea is to bring harmalol close to its isoelectric point.
- Pull with EA. An emulsion formed, but sending it through a coffe filter cleaned it up easily.
- EA salted with citric acid, massive cloudiness on 1st pull
- Red goo precipitates. Is this mostly harmalol citrate?
- Decanted precipitated EA, rinsed red goo with fresh EA, and dried
- Got about a gram. This would be about 500mg of harmalol. I imagine after a few more pulls it could be 1g of Harmalol candidate (2g of goo).
- 700mg of goo (~350mg of Harmalol?) dissolved in warm PG easily (first image). Resulting e-juice is highly flourescent (second image).
- Added 350mg of DMT using 1.7g of the e-juice made with this TEK
- Had a few ml of a harmalol-DMT ejuice candidate. It is a beautiful red color.

Next I will test by vaping. If effects are good (hoping for a longer harmala like vaped DMT experience), I'll send some of the combined e-juice for analysis.

Is harmol in there as well? That might be easier to pull from the solution as it freebases at the lowest pH, and this minimises the risk of deprotonating that phenolic hydroxy group. I'm sure you'll have thought of that already

[Incidentally, there is a component of Peganum harmala alkaloids that seems to be slightly soluble in butyl acetate after salting with citric acid.]

Have you tried any vaping tests with this stuff yet?

Could be, going by the wikipedia summary seems like harmol has not been reported? The summary could ve incimplete of course.

I did some shy vapes. Seemed ok. Need to try more of it becaide I really did some sjy hits only.

What makes you think that about butil acetate? Curiois as to what you are seeing. Cheers.

Loveall/ DFZ,
I'm not good at reading LC-MS results my understanding of cleaved function groups etc is not good currently (I'm slowly learning when I have time). But could the LC-MS results from the EA harmala approach indicate harmalol?

There's a tiny indication at the 200 mark and couldn't the peaks at 168 indicate harmalol with OH and NH cleaved?

Am I interrupting and understanding this right?

The 168.21 would be spot on for Harmalol missing NH and OH groups. Can NH be cleaved?

I know as stated it may just be Harmaline missing CH3 and OCH3 but could both harmaline and harmalol be indicated in the results? It is a narrow margin between the two and potentially indicated.

Hard to say for me. There are published spectrums and calculated ones out there.

See image below from attached paper, hopefully this example helps. For harmalol, there is a peak for a cleaved OH group at 201-17 = 184, and the molecule is drawn. Then are two small peaks at ~174 and 169 (maybe your 168.2 question), likely from cleaing C-CH3 and (CH3,OH) respectively, but these structures are not drawn so not sure. I'm surprised the 186 peak from simply cleaving CH3 is missing. There is a large peak at 160, and in the drawing the entire N=C-CH3 section of a harmalol ring is cleaved. Finally in a second plot there is a peak at 132, and a totally mangled harmaol missing both C-OH and N=C-CH3 is shown.

The relative intensity of the peaks can change with machine voltage settings. Maybe lower voltages cleave less. Maybe intermediate voltages have bigger peaks for the first cleave combos. Lower voltages may have the uncleaved molecule as the most intense peak, IDK.

Inspecting the image below it does not look like the N-H group at the core center of the molecule is cleaved for harmalas. Instead, what gets cleaved are the dangling edge CH3, O-CH3, and OH groups, together with nearby chunks ring sections attached to these groups.

Nice find, interesting.

So there's a possibility there are other configurations of cleaved groups that are not listed?

Either way, that paper offers some valuable information.

Correct, there could be otber cleavings not listed in the paper.

A solution of ammonia-precipitated harmala bases was made using butyl acetate. After precipitation of the alkaloids as citrates using excess citric acid, a yellow-green fluorescence remains visible on illumination with the spy pen. The concentration is low, as can be inferred from the penetration depth of the light beam. I have not attempted to isolate any solid material yet.

I can imagine that harmine or harmaline citrate might well be a bit soluble in butyl acetate because their lower base strength of those alkaloids makes it more likely for dissocation back into the free base and free acid to occur. There's a huge number of experiments I need to do now that summer is drawing to a close over here.


_Trip_ - I'll have a think about your MS question, not least because I really ought to improve my grasp of that field myself.

You'll notice here how this plausible cleavage gives a molecule of acetonitrile. The phenolic ring of harmol spits out a carbon monoxide in scheme D1.
Are there machines that produce a pseudo-3D plot of a voltage sweep scan? That would serve to highlight what you're describing here.