SWIM remembered another dream about syrian rue extracts.

After doing some precipitations (NaCl + NaCO3) on syrian rue extracts SWIM had brown powder which contained mostly harmine (+harmaline). After making more basic and precipitating SWIM had a yellow powder which contained mostly harmaline (+harmine). This was checked by GC-MS.

After recrystallizing the brown powder in ethanol a red substance remained dissolved in the ethanol. From this red substance more harmine and harmaline was precipitated (lower volume recrystallizations got more out). Much less harmine and harmaline was present in this red gunk after doing this according to GC-MS. Before I cleaned the red stuff up there was still harmine and harmaline hiding in it.

So SWIM did some various analysis with derivitized samples on GC-MS and saw nothing.

Then SWIM started thinking ok maybe its some kind of phenolic or tannin like compound. So SWIM mixed this red stuff with alcohol and some water. When dilute the solution was orange. SWIM then used Ferric Chloride (a reagent that tests for phenolics) and the solution turned deep red / green which usually indicates a positive hit. For controls SWIM mixed ferric chloride with harmaloids in solution and there was no color change SWIM also mixed ferric chloride with pure phenol in ethanol and it turned brown indicating the reagent was working.

Therefore SWIM thinks its possible that this red stuff that everyone has been calling harmala red is an impurity in syrian rue seeds which is highly soluble in ethanol. There is no evidence that this red material is a breakdown product of harmine or harmaline as that should have been visible by gas chromatography. Furthermore there is evidence from a color reagent test that this stuff might be a phenolic compound.

Thats all for now. Further spectroscopy using NMR or IR would help figure out what this stuff is but thats alot of dreaming.

awesome burnt! but, question.. if it was impurity and not degradation product of harmialine, then how comes it can be made when one has pure harmaline and redissolves it in alcohol and it turns red? It took a few redissolving and evaping for a considerable amount to turn red, but it did happen with pure white harmaline for me...

That's some excellent chemistry there! Is it feasible to run tests for other functional groups, like for esters with Iron(III) hydroxamate, or for aldehydes/ketones with 2,4-DNP?

I hate that you can't get IR or NMR spectra...

More dreams:



In this case the red stuff was purified from a precipitant that according to GC was mostly harmine. Note that GC doesn't see this red stuff so in reality its probabaly not pure. The harmine base was a dark brown when it was first precipitated. After recrystallizing with ethanol and removing the red stuff it became a lighter brown.

Basically the conclusion is that when SWIM was precipitating the harmaloids this red stuff came with it. It could have simply been the red stuff not filtering out and being stuck with the harmaloids on the filter. Anyone who has done these extractions knows how hard they are to filter. SWIM has in the past made extracts of harmaloids that were not so brown so maybe those ones had less impurities who knows? Its too late to analyze that older material however..

SWIM has noticed that precipitants that are brownish contain more harmine and ones that are yellowish contain more harmaline.

However in your case you said you got the material to turn red with pure white harmaline yes? That could throw my entire theory upside down. SWIM has never had >99% pure harmaloids and never deliberately exposed them to ethanol so can't say for sure. How does SWIM know the material was pure? color? Did all the material turn red or just some of it?

Certainly makes things more confusing but also interesting. SWIM is curious how come many synthetic procedures for harmine and harmaline use ethanol or methanol to recrystallize if it would cause impurities to form or degradation?





SWIM was thinking to do thin layer chromatography and then use a few reagents like fast blue B and maybe some others like vanillin to observe what compounds are present. But SWIM has no free time to dream for a bit.



Its not so much aquiring the spectra as it is interpreting it. NMR spectra of mixtures (assuming this red stuff is a mixture of impurities) can be extremely complicated and time consuming.

It all comes down to time really..

yeah what I did was have very white harmaline that was obsessively purified with god knows how many manskes (at least 7) and god knows how many base precips (at least 5), with a lot of thorough filtering in between when it was dissolved in solution to remove non-actives.

So what I did was just add warm IPA to that harmaline that was in a petri dish over a yoghurt heating pad (cant be too warm, maybe max 30 degrees celcius or smt) and evap the IPA.. I spilled a little bit of that IPA on the heating pad and the part that spilled evapped to become a red goo.. funnily enough the harmaline inside the petri dish got a bit of a red tint to it but not much (maybe IPA wasnt the best way to test, it is poor at dissolving freebase harmaline, I wonder how acetone/ethanol/anything else would be). So I redissolved a few times and evapped again and every time it got a bit more red, but still there was considerable amount of unchanged harmaline, judged by it being very crystaly, unlike the red goo that formed on the spilt part..

it was most definitely something that was NOT in the harmaline but that formed from being redissolved and evapping.. harmaline oxide maybe?

I had separated the harmaline from harmine by precipitating harmine first with sodium bicarb

I used USP grade 99,5% IPA


Ron had a nice macro picture somewhere of this red goo forming from harmaline HCL

Ok that may clear things a bit anyway.

Precipitants in the dream were mostly harmine for this recrystallization. The harmaline was left alone (the yellow crystals look nice ).


Still SWIM is very curious that is actually changing if harmaline is degrading? What could alcohol cause to happen like that on a beta carboline?

Either way to solve this mystery more experiments need to be done. But at least now SWIM is more clear on what others have observed and therefore what needs to be answered.

Nice.


Does anyone know what happens if you extract syrian rue seeds with just ethanol and evaporate them what it looks like?

Could be that alcohols help turn harmaline to harmalol (which is a brown/red crystaline phenolic) or help extract more of it since it is present in quantity in Rue seeds.

Hmm... well, NMR spectra of mixtures would certainly be a bummer, but an IR might be more helpful.

Would TLC or some other technique make it feasible to separate the red stuff into multiple fractions of pure products, and get NMR for each of those fractions?

Well I should be more correct. In a few minutes of looking at NMR spectra even if a mixture it can be obvious what KIND of compounds are present. But full structure elucidation can take much longer.



Yes the normal way of going about this is:

Develop good TLC system to separate components using silica gel TLC plates.

Then run a column with silica particles to separate components. A column has higher loading capacity when compared to preparative TLC plates and thus you can load more and get more yield.

Then check purity of fractions with TLC or some other method.

Then pool the fractions that contain only the compound you want.

Dry them weigh them. Analyze.

The only problem? Time.



SWIMs first idea is that it might be harmalol. It still might be. SWIM is just curious though because harmalol should be in GC-MS chromatogram especially after derivitizing. SWIM just doesn't see it. SWIM can play around more with derivitizing conditions and trying to form something thats analyzable but again the problem? Time.