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'harmala red' LC-MS analysis

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burnt

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Senior Member
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SWIM had a dream.

An extract of peganum harmala was made with acetic acid and water. It was basified with sodium carbonate and salt. After precipitation a brown residue was obtained. This was recrystallized once in ethanol. After brown crystals formed they were filtered. The supernatant was dried. It was red. Swim expects this is what people commonly refer to as harmala red?

SWIM analyzed this material by LC-MS using APCI probe operating in positive ion mode. UV measured at 254nm and 380nm. C18 column methanol water gradient...details not necessary at this point.

The results were mostly harmine and harmaline. As well as some harmalol and some unknown compounds.

SWIM has not analyzed the initial material. Next time when SWIM has time to dream SWIM will analyze the initial extract, the recrystallized material and the supernatant. To determine a bit more whats going on.

Note SWIM has also analyzed this material by GC and its also mostly harmine and harmaline SWIM can't remember if harmalol was there.

Anyway it seems yet again what we thought was going on: degradation, or some major impurity is unlikely. But more experiments need to be done. I post a UV chromatogram with relative % abundance of major 3 harmaloids.
 

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Questions: Does the analytical method tell the difference between harmine/harmaline n-oxide and the parent compound?

Question 2: What about vasicine vasicinone? When you said it was purified with 'sodium carb and salt' does it mean you salted as mansk (and hence why they dont show) ?

Another thing. From what I understand the brown harmala that you dissolved in alcohol was freebase, yes?

What about doing the same with hcl salt? and what about doing it with successive redissolutions and evaporations ? I ask these questions because from the tests I still dont get the answer to my main suspicion: Its oxidation of harmaline (and maybe harmine), which might happen more likely with successive evaporations.

Thanks for sharing the tests burnt!
 
N-oxides can show up in 2 ways. Different retention time and different mass. The mass might be hard to detect because it may depend on the ionization conditions. They may need to be optimized to detect the n oxide. The retention time would be easy to compare if SWIM had regular harmine and harmaline to compare. SWIM hasn't dreamt about this yet. Another night another dream.
 
Hmmm. ~2:1 harmine to harmaline. That means when SWIM further purifies his Manske derived product of P. Harmala he can expect only 1/3 (net) to be harmaline. Cool. SWIM wants to do this and then try reducing his resultant harmaline to THH using electrolysis, as he suggested might be possible in another thread. Gonna get going on this is a week or so.

N.B.
 
Is there any evidence that harmaloid n oxides even exist at all?

I always thought the O often gets placed on primary amines not tertiary amines. I could be wrong about that though. Anyone know?
 
Nature Boy said:
Hmmm. ~2:1 harmine to harmaline. That means when SWIM further purifies his Manske derived product of P. Harmala he can expect only 1/3 (net) to be harmaline. Cool.

Alkaloid content can very a lot between batches of syrian rue. So the 2:1 ratio is not a contant number at all.


Kind regards,

The Traveler
 
The Traveler said:
Alkaloid content can very a lot between batches of syrian rue. So the 2:1 ratio is not a contant number at all.

Kind regards,

The Traveler

SWIM's FOAF understands that to be the case - as with virtually all botanicals. Still, its nice to have a reasonable approximation so that there is no concern that something is amiss right at the outset. Does anyone have an opinion as to whether this is a good experiment to undertake (reduction of harmaline to THH with electrolysis) or is it simply wishful thinking? SWIM's friend has a very reliable regulated power supply, materials and equipment to employ in the endeavor if the consensus is that it might be fruitful to proceed.

Again, best to all,

N.B.
 
Nature Boy, waht is your setup going to be?

I suggest making a seperate thread so this one is not cluttered up. I am following also this thread very closely i wonder if the unknowns could be identified. An idea would also be subsequent multiple redissolvings in alcohol and evaporation of it, checking each time how (IF) the peaks are modified.
 
It would be hard to ID unknowns without having an idea on what they might be. Lots more experiments need to be done. This is in no way conclusive but brings up lots of new ideas. It will be a while before SWIM has time to dream about such experiments again.
 
burnt said:
SWIM analyzed this material by LC-MS using APCI probe

out of curiousity...why APCI? any advantage to using this interface over standard ESI with these compounds?

with standard ESI, solvent gradients using 0.1% formic/acetic may be employed. the extracted free base is effectively transformed to salt form, with cleanup/separation mostly occurring at the column.
 
These results match my own yields/bioassays when playing around with harmala red while doing syrian rue extractions. As whiterasta's tek uses alcohol and I use a computer fan to reduce this solvent when going this route I have formed large quantities of harmala red which I treat no differently than the liquid part of the extract. I have never found the yield or potency to suffer when done side by side with a manske using seeds from the same batch. I just ordered a pound of rue and could post pictures of such a side by side extraction between a manske with no harmala red and a whiterasta with large quantities of harmala red to further support burnt's analytical findings...not that it would be necessary, but it could be interesting.
 
sorry for digging up this old thread.. but i'm interested if anyone has done more analyzes?

i think for those who're making changa, and had to dissolve harmalas, its still an interesting question

- is there oxidation to harmala-oxide, or not?
- if yes, is harmala-oxide more harmful? or only loss a bit in potency?

RF
 
I don't think any more research has been done on that, and at the moment I'm pretty busy for it but if you remind me again in a couple of months I might get onto that.

My gut feeling is you have nothing to fear if youre just dissolving and evapping for changa, change is probably minimal if at all. If you were keeping it for extended periods in alcohol, under heat etc, then it might be different. But in any case more tests are always good, something to keep in mind for the future of Nexian endeavors :)
 
RideFree said:
- is there oxidation to harmala-oxide, or not?
- if yes, is harmala-oxide more harmful? or only loss a bit in potency?
Harmala red exists and is used for dying purposes. Harmala red does not, according to burnt's analysis, present any significant degradation when compared to harmala alkaloids.

In other words, it may look different, but it's essentially the same.
 
thanks endlessness & SnozzleBerry! so i think everything is alright with my IPA-Changa

i'm only a newbi kitchen chemist, for me its impossible to do research with professional hardware.. for those like me its very important to have professional chemist like you guys are..
thank you for that!
 
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