Harmaline 'slightly soluble in basic water'?

[Elrik]

Any time I base mixed harmalas the filtered motherliquor is a strong vibrant yellow from dissolved harmaline. I've often read harmaline is 'slightly soluble in basic water' but has this ever been quantified at all? I've seen 'slightly soluble' refer to 1% solubility with some authors.
As a casual proof of concept test I took an aliquot of such motherliquor, added an equal volume of 91% isopropanol and saturated the mix with salt. Most of the yellow migrated to the alcohol layer in room light and most of the neon green migrated to the alcohol layer under blacklight.
Has any effort been put to quantifying the solubility of harmaline base in pH ~9 ammonia water or seeing how much can be reclaimed without extreme measures?
I'm wondering if I could distill off 3/4 of the water, do two alcohol pulls and some follow-up, and manage to get an extra half gram of mostly harmaline from this liquid.
I have 2 kilos of harmala seed so I'm not desperate for yield but I recycle all my solvents so all I'd waste is salt and time :lol:

 

[doubledog]

Ime, pH 9 is too low to precipitate what is left in this yellow solution. If it is still strongly yellow, you could obtain a lot of alks by basing it with some stronger base.

 

[Jagube]

Yes, at pH 9 a lot of the harmaline is in salt form.

I don't know harmaline's solubility, but here is something that speaks to its insolubility:
When extracting rue seeds (I do 400 g at a time), I base the combined boils without reducing them. This 400 g seeds worth ends up in 10 liters of basic water.

This still yields ~6% post-manske, with roughly a 45:55 harmine:harmaline ratio, so it doesn't look like a lot of harmaline stayed in solution in the initial basing.

 

[Elrik]

Good catch :lol: Okay, forget I said ~9, a 'firm 9' is where I know I'm done when testing with my low grade pH papers. I should never report numbers from these crude papers.
I tested the filtered motherliquor with my actual pH meter and its 9,65.
I took a 5ml portion and added a generous quantity of NaOH (aq) and the yellow color instantly cleared and after two minutes no haze or precipitate formed. It acted as though, yes, some or all of the harmaline was ionized as you say [probably half, since that's nearly its pKa], but when based it was still within the soluble range.
Harmaline glows so intensely I'm not sure just how much is needed to make an intense glow under UV. After working with this stuff it looks like a rave vomited on my hands and arms, I've even painted designs on myself with the waste :lol:
[LSD synthesis would be wild for me if I did it like I do harmalas]

here is something that speaks to its insolubility:
When extracting rue seeds (I do 400 g at a time), I base the combined boils without reducing them. This 400 g seeds worth in 10 liters of water.

Man, some time when I'm feeling playful I need to compare your method to mine. You had me at no reduction.

 

[Elrik]

Well I proceeded to experiment with this waste and was unable to recover anything of use, even after notable concentration. So I feel better about dumping it, now.
To my surprise I also isolated an untestable volume of volatile oil from my 4X mansked harmalas. It seems volatile plant oils may 'stick' to harmala•HCl.
Details:

Spoiler

13 grams of mixed harmala•HCl was dissolved in distilled water and based with 10% ammonia, after filtration the 425ml of liquid waste had a pH of 9,65 and glowed vividly under UV.
This solution was concentrated by distilling off 315ml of water, the ammonia went with it and a drop of an unknown steam volatile oil also distilled over. The remaining 110ml of liquid now had a pH of 3,61 presumably due to ammonium chloride. pH was brought to 9,30 with sodium carbonate.
60ml of 91% isopropanol was added and the mixture saturated with salt with stirring. Nearly all color migrated to the alcohol layer in room light and under UV. The alcohol extract [espresso colored] was isolated, a second alcohol pull was done getting most of the residual UV fluorescent material [the resulting alcohol pull was amber in color], and the pulls were combined.
150mg of citric acid was added. 50ml of distilled water was added. The alcohol was fractionally distilled off, leaving 50 ml of a red solution with a pH between 5 and 6 and containing some red-black solids. The small amount of solids were filtered out and 30ml of saturated salt water was added. The solution was chilled and left in an ice bath for many hours. Another small quantity of the red-black gunk precipitated from the now amber liquid but no alkaloid hydrochloride crystals formed. The solution still fluoresced under UV, but not as strongly as before.
The combined red-black solids were not measured but amounted to very little actual weight.
Experiment concluded.

I'm really starting to think that the red-black solids often encountered in work with rue alkaloids are an oxidation product of the alkaloids rather than residual plant gunk.
I'm looking forward to trying Jagubes method now, as a bonus I'll finally get to play with the accessory alkaloids without much extra effort at all.
I wonder if I'll find a practical use for vasicine.