Conversion of Harmine->Harmaline->THH by simple boiling (and storage?)

[downwardsfromzero]

Hmm, that's pretty interesting research. We've strayed a little now but my line of thought brought up this article:

What Hydrogen Has to Do With Healthy Gut Microbes and Reducing Inflammation

The latest health fad among the Hollywood elite, Silicon Valley, sports and biohackers is drinking hydrogen water. But you don't need to pay from $6,700 to $10,000 for a home hydrogen water system. Or around $80 a

www.chopeglobal.com

"However, it’s clear the most effective (and cheapest) way to increase the hydrogen gas in your body is simply to eat more plant foods."
And this:
"[...] two bacteria lines that play a direct role in IMO are Ruminococcus and Chris[t]ensenella organisms. These two bacteria lines make hydrogen gas [...]"

Intestinal Methanogen Overgrowth (IMO) - Dr Robert Brody's Medicine

Physicians have long known about SIBO, but IMO is new to researchers. Based on archaea, not bacteria, this diagnosis needs a new treatment plan.

brodynd.com

Back on topic (nearly), I'll dump this link here as a reminder to work out the arithmetic of the hydrogen peroxide reduction question:

Table of standard reduction potentials for half-reactions important in biochemistry - Wikipedia

en.wikipedia.org

 

[ShadedSelf]

Re-reading proffesor8's post, his claim - or the one he reports from Nobuoni, at least - is that dissolved oxygen acts as a transfer agent of hydrogen form the ascorbic acid via the formation of hydrogen peroxide. And yes - H²O² can absolutely act as a reducing agent under certain conditions, such as when it reacts with permanganate, for example.

This would appear to imply that simply adding H²O² to the (acidified?) harmaline solution should achieve the same end (whatever the result may actually turn out to be...) It also implies that the pressure cooker anvironment may be less than optimal for the ascorbic acid reaction if dissolved oxygen is required as the hydrogen transfer agent.

And indeed, that's what Nobuoni suggested here. For me the main question might be - do we think any of this is worth revisiting?

The first thing to do is probably checking on the reduction potential of the reaction

H2O2 → 2H+ + 2e- + O2 Eo = -0.682 V

The thing is, hydrogen peroxide tends to perform more effectively as a reducing agent under alkaline conditions, and this reaction (the putative reduction of harmaline) is being carried out under acidic conditions.

Right now, I'm not off the top of my head able to convert this electrode potential into a molar reaction energy to compare with the energy value for the reduction of the imine double bond in harmaline but I'll attempt to remember to check it out once I've had a night's sleep.

I prepared a solution of harmine/harmaline mix with 5% H2O2 (not sure what the rest is) and vinegar the moment you posted this, not sure if this is exactly what you suggested but...

The solution now glows dark blue under a 365nm UV light, shines similarly to my THH and darker than my harmine, though I think there might be some harmaline in my harmine batch.

It has taken its time but its now definately different that a solution I just made of that same batch of harmine/harmaline mix, so something has clearly happened, I wonder if its just harmaline turning itself back into harmine though, Ive left the new solution to sit and see if that change in color happens without the H2O2 over the following months.

 

[downwardsfromzero]

Very interesting result, ShadedSelf. You should consider checking it with TLC. It may be time for me to try this putative reduction myself.

Downwardsfromzero, your pc cooker acts just like the reflux pot setup made by Professor8 when he reduced harmaline to THH in 2 hours using very pure ascorbic acid (you can buy 100% pure ascorbic acid on-line, only use this). Ingenious! Great work. Test the glow under blacklight to see if she turned from the harmaline green glow to light blue of THH. Dab a cue tip in vinegar, take up some of the harmline/THH, smear on a paper plate, hold under UV light...if you have blue glow, then you made THH.

I used pure ascorbic acid powder, which is available off-the-shelf in my part of the world. The conversion is not complete, because there's still a yellow-green harmaline glow to solutions of the material. I could attempt a further reduction of the crude alkaloidal material by cooking it with a further amount of ascorbic acid but at this stage a TLC analysis would be the most informative step.

I'm also planning a replication using higher amounts of vitC (and at a lower temperature, based on Jees' comment), and another batch using none. It's just a question of priorities at the moment.

Also worthy of note is my current thinking that ascorbic acid may conserve harm(al)ol in the brews as much as doing anything else. I will nonetheless try simmering purified harmaline with a concentrated solution of ascorbic acid sometime, however.

The figures for reduction potential still need looking into - any other takers for a bit of chemical arithmetic? There's a few other things I ought to do first...

 

[ShadedSelf]

I dont have any TLCs, but I could probably tell you if there is any THH in there just by looking the freebased alkaloids.

How would one retrieve the alkaloids from here?

 

[downwardsfromzero]

Are you planning to use microscopy? You can watch the crystal formation after adding ammonia to a drop of the alk solution on a microscope slide - there was a thread about this, or maybe it was in the VDS protocol thread.

The VDS protocol thread details how you can recover the alkaloids separately.

 

[ShadedSelf]

I was more concerned with H2O2 reacting with particular bases.
Souns like ammonia is safe.

No mycroscopy, in my experience harmine forms a brownish, fluffy powder, THH a white and dense one.
Assuming there is just one or the other in there should be easy to tell.

Ive based the solution with ammonia, havent dried it yet but all I see are small brown needles, pretty sure there is mostly just harmine in there.
Not very scientific, but the best I can offer right now.

 

[Jan e Kharabat]

in my experience harmine forms a brownish, fluffy powder, THH a white and dense one.

In my experience, pure enough harmine can also be white and fluffy. There are some "impurities" (by impurity I refer to everything aside from harmine, harmaline and THH) which fall out at lower pH, so the brownish color of harmine is likely because of that. To assess properly, you should separate harmine and harmaline, do further Manske on them separately (or even freebase recrystallization with IPA if you will), and then basify and check the texture. In my experience, freebase THH doesn't differ that significantly from harmine and harmaline, but THH-HCl is quite different, it doesn't form long sharp needles or fluffy hair-like structures but more like... the flora at the see-bed. Also, the texture is more brittle.

 

[ShadedSelf]

Thanks for the input.

I assumed little to no impurities, the starting material was fairly clean.

I acidified the alkaloids and added a bit of NaCl, white crystals started to form.
I know Harmine and DHH HCL together form golden needles, and looking for images of their HCL salts separately does seems to indicate that both have that golden color individually.
THH HCL forms in small white crystals IME, so looks like it its THH after all.

The manske filtrate had a red color to it and upon basifying a bit of dark brown/reddish stuff started to precipitate, no idea what this is or where it came from.

 

[AwesomeUsername]

Really late here but this might be true.

Recently I did just that.

Cooked for a really long time with some citric acid, left it to stay, cooked again, filtered the seeds, reduced everything to a syrup, pulled with ethanol and it was a huge difference.

It didn't feel dirty, sludgy and like something was off and wrong.

It turned my mood from annoyed, and exhausted to relieved, carefree and almost euphoric.

Never had a huge dose of harmalas on their own or tried pure THH, but the feeling made me think a big part converted to THH, it truly felt like a bliss.

My preference is to keep harmalas on the low side, to prevent feeling sick, but even at low doses, no bodyload what so ever yet a significant mood boost. Changed my opinion on rue seeds after just a single dose. Would recommend to anyone to try it, although the preparation was messy, long and all over the place, it was well worth it.