Now I will apologize immediately first of all for having a title with such a definitive answer over-top of some dodgy "science". Though here' is what was done to 'conclude' this. *Note* this is not a tek, but if you would like I can include the preparation for the reagents used in this reaction from OTC chemicals. Although, it might be against the board's safety policy to mention how this one made concentrated ammonia.

The red harmala was extracted from some 'crude' looking harmalas that came out of attempting enoons ethanol recrystalisations.


After doing a manske on the crude harmalas, the NaCl saturated water was slightly diluted then basified(on the left) while the clean harmalas precipitated(on the right). Notice how harmala red floats on the top?:idea:


edit - the paper for this can be found here https://www.dmt-nexus.me/forum/default.aspx?g=posts&t=20670


From the original article: 8mg harmala red, 2mL conc. NH4OH, FeSO4(excess), Heated on steam bath for 30 minutes.
Some preliminary Calculations:
Harmine-n-oxide: 228g/mol * 0.008g = 0.000035088mols
FeSO4: 152g/mol * 0.000035088mols = 0.005333376g(but use excess)

What I used: ~0.2g(wet with residual H2SO4)FeSO4 and ~30mg harmine-n-oxide and 7.8ml conc. NH4OH(extra because of H2SO4)
Experimental:

No point in showing the scale it read 0.0g(can't read mgs).


Freshly prepared FeSO4, crystals were beautiful but were broken down to remove from flask.

FeSO4 and conc. NH4OH were added to a 100mL round bottom flask and given a quick spin. Shortly there after ~30mg of the 'red harmala' solid was added. The solution flask was set on top of boiling water. The reaction mixture bubbled away releasing NH3 fumes.



After a half an hour of heating the flask was removed. Extracted 3x 15mL with warm toluene. The combined extracts were added to a seperatory funnel and washed twice with NaOH solution 2x. Then the solution was shaken 10mL of citric acid solution. The citric acid solution took on a classic blue/green of acidified harmala water. The aq layer separated, and organic layer shaken with another 5mL of acidified water. The aqueous extracts were combined.



To the aqueous extracts 0.4g of solid NaOH were added. And shaken until full dissolution. The flask went from harmala color to a clear solution. No precipitate was evident but the solution was hazy and left to sit. Later on, no precipitation formed but the solution cleared up.

Attempting to find the desired precipitate the original reaction mixture was filtered through cotton balls(to remove the iron complex). An iron colored orange solution remained. The solution was then acidified with citric acid and filtered again. There was no change in the color of the solution. Solid NaOH was added to the filtered reaction mixture. NH3 fumes evolved and two precipitates formed. One on the bottom of the solution(white), and one on the top slowly built itself(pinkish white). By built itself it is meant that over time, it slowly grew as more crystals from the solution found their way to the top, there was a definite attraction in the compound(s). It probably floated to the top because of the NH3 gas being evolved from the mixture, forcing the ppt to float upwards. The solution was left to sit for several hours. Then filtered. The precipitate was off-white/tan and when heated by lighter within seconds melts and boils(not ionic). The collected yield was much smaller than the reactant.


That's the pitiful yield. You probably can't see it in the picture, but the scraped filter paper shines from crystal deposits .

On cleaning the reaction flask with vinegar water the water also turned harmala blue/green. Though this was realize several hours after it was dumped down the drain . This could account for a lot of the loss. Or it could have been iron acetate, although, if all of it was, then were is the harmala-red?


Here's a picture of the flask after being cleaned with vinegar, it is now soaking in dilute NaOH solution . As you can see there is a brownish residue on the walls, most of it probably being iron, but before there was a lot more that quickly went into soln. with the vinegar.


End notes:
Some things I'd like to change, would be to recrystalize the harmala red in methanol and have more of it to run melting point tests with. Also to use ether to pull from the reaction soup instead of toluene as the procedure in the paper suggests.

So is it really harmine-n-oxide? Well it's hard to say, it appeared to be reduced(from red to tan), but I have no means of actually testing these tiny flakes. So it would be excellent if a real chemist tried this out as well and could back these results or disprove them.

Nice job, but it could be that you could have only extracted a tiny amount of harmalas trapped into this harmala red or that you've reduced some harmine-N-oxide to its parent compound.

The whole experiment sounds pretty inconclusive, but you could have attacked the problem better should you had used a control, which you didn't do; you should had made n-oxides of harmalas by treating them with hydrogen peroxide (as described in the paper snoozelel attached) and then reduce them and treat these n-oxides as your harmala red. You'd check how efficient is your your reduction method and you'd be left with far less ambiguities....

There's really not something more important than controls in science. And you can never have enough.

I once heated manske alkaloids too much in front of an hot oven and they started turning into red goo,
my conclusion was harmala red is burnt harmaloids

Totally agree infundibilum, it is pretty inconclusive although a dark red powder(harmala unknown) to a tan/white/pink powder seems like there is some 'suggestion' this is what it is. There will be more tests done on this in the future. With controls, I suppose I could prepare some harmine-n-oxide as well sometime over the weekend, just gotta concentrate some H2O2. Really, really don't want to work up any ether although I wouldn't need much so maybe I will anyways...

Guess the main point of this thread was to re-inspire interest in the 'mystery' as well has have an idea of what the reaction was like. Eventually... I'll have enough money to buy some silica and microscope slides to maybe do some TLC and check RFs. Before and after the reaction.

Should I prepare some harmine-n-oxide, run the reduction. Then prepare some harmala-red by ethanol evaporation and run the reduction. Then check RF's before and after as well as melting points? That's probably the best I could do at home and not in a laboratory.

Observant - Interesting conclusion and all, but isn't heat in the presence of oxygen a cause for oxidation? So I think your actually supporting this notion with your statement.

Also when harmalas are put into an evaporating dish and covered with acetone then left to evaporate a ring of semi-crystalline harmala red forms on the dish. Surely no heat is made when acetone is evaporated by air circulation only.

yes- i wanted to support your conclusion mydriasis - i think youre right!