I've been wondering what solvents can be used for the recrystallization of Harmine and Harmaline freebase. I've read that methanol and ethanol can be used, but ive also read that produces inactive "harmala red", which I would like to get rid of if it is in my end products. So how do I go about this? Should I just do as in a recrystallization of DMT except with methanol? I also read it can be chrystallized from hot chloroform but I don't care to mess with that. Why is there not more solubility information on harmalas?

what is the purpouse of the recrystallization? Is it for purity? Or is it because you want to grow some nice looking crystals?

If its just for purity, the way thats usually been done is to redissolve the harmalas in warm acidified water, filter several times to remove impurities, and then re-precipitate by adding a base. Each time you repeat this process it cleans it up more and more.

As for why there isnt more information about it, the simple answer is because tests havent been done or havent been shared. All the knowledge in the nexus wiki and forums were made by people who made own tests and comparing with literature data. There are plenty of tests that can still be done which will be great for our community, and all it takes is someone with the possibility and desire of doing.

So if you wanna make some solubility or side-by-side tests in the future, dont forget to share the results

Thanks for the reply. I have thought about doing tests but don't have reliable means to measure things like temp or ph. I am the epitome of the "kitchen chemist" another year and I'll have my PhD .

However I do have Naptha, Heptane, Acetone, MEK, Xylene,and DCM around, and can easily get 99% MeOH and 95% EtOh, along with severa grams of light tan harmine and harmine with which to do some tests. I may do that. Oh and I will have Ethyl Acetate in soon as well. That would make for a good sum of data. Wouldn't it be great if a relatively common solvent could grow pretty white harmala shards?! Thats really what I'm after is pretty xtals.

Well, you have a nice array of solvents! Try also making different salts of harmala: sometimes one salt might not crystalise that well whereas another might make beautiful crystals. Over the counter you can find easily citric acid , hydrochloric acid, fumaric acid, tartaric acid,ascorbic acid, acetic acid even sulfuric acid. That should give you a range of salts to study.

As for endlessness saying that the lack of information is because that tests havent been done or shared i have to agree. It takes some people to start playing and sharing their results and you start seeing threads like those : https://www.dmt-nexus.me...aspx?g=posts&t=13886 . Another factor is propably that many people might not be that interested since rue and caapi work easily is teas, or a simple "salt and vinegar" extraction yields a product which can be considered suitable "as is". Add to that the trend that people will buy what they can find commercially instead of going DIY, and that harmalas are commercially available saving one from "laborious extraction procedures". Hmmm, if other products -such as "cacti tar", "mimosa concentrate" or "purified extracts of their active principles"-were commercially available because they were legal most people, save the ones genuinly interested in extractions, would forget even that water is a solvent .

I suggest looking up the theory behind re-xing: factors affecting recrystallization such as eavaporation time ,temperature, etc. This would be a good start to give you some ideas saving you at the same time the time of possibly reinventing the wheel. You could try recrystalissing different salts of harmalas from slow evaporation of distilled water, or alcohols. Also i wonder about harmala solubility in those solvents you mentioned (acetone especially, MEK and propably ethyl acetate)

SWIM recrystallizes in ethanol. Its recommended in the Merck index.

However the solvent used for recrystallizing does dissolve some red compound. SWIM does not believe this compound is a breakdown product of harmaloids. There is no proof of that. Its possible but SWIM is doubting it more and more. SWIM thinks its more likely the red compound is an impurity that's always there in precipitation extraction methods.

Relevant threads:

https://www.dmt-nexus.me...aspx?g=posts&t=16766

https://www.dmt-nexus.me...aspx?g=posts&t=11077

Crystalito- All in due time. I'm not a REAL chemist so that will take a lot of playing around. I only have experience with bufo & dmt fumarate. I never really worked up the skill of growing big fum xtals because I usually was after the fb and wasn't worried about the getting that big.

burnt- Yes I read those threads and am on your side about the "harmala red" being natural dye from the seeds. That is what they are technically sold for after all. Maybe my test will find a solvent that will leave it behind. Have you ever ran any tests on the red "stuff"(technical term) to test its solubility?

mombreast-The merck index for harmine says slightly soluble in alcohol. You've shown that it isn't? Did you boil the alcohol?

What are plant materials? Impurities.. So if you remove any oils or plant matter that is not alkaloids, you are effectively removing impurities, so I dont understand what you're saying. Did you ever do successive base precipitations? Its pretty obvious ime that its cleaning up the alkaloids each time.


Burnt, regarding harmala red, as I said and Ill say it again, while I understand your argument that in some cases it might be some natural red dye from the seeds, in my experience thats clearly not whats happening in every case. As I said before, I had very white crystals and successive redissolutions and evaporations of harmaline in IPA turned it into a red product. You counter-argued that it might have been some impurity that was trapped inside the crystal and it came out, but that was definitely not the case because it wasnt a tan powder becoming slightly more orangy or something, it was a very very white powder becoming much redder.. Too bad I didnt take pictures, and right now im not in the situation to do these tests.

If anybody is interested, just do it yourselves.. Dissolving and re-evap harmaline (maybe harmine too, dont know) many times with hot IPA (maybe ethanol too?) and plenty ventilation. It happened with freebase harmaline for me, but I remember seeing a picture that 69ron showed this happening to harmaline hcl and alcohol (I suppose he meant ethanol)

Could it be that there is an impurity that is white but turns red when exposed to hot alcohol?

^Thats what I was thinking. Even product thats appears white can still have fats and dyes trapped inside that can't be seen without being broken down like in a re-x. I've had some of the whitest spice I've ever seen turn heptane yellow during a re-x. Could this not hold true for other substances as well? If it wouldn't then please correct my thinking on the matter.

you two are talking two different things. If an impurity was white and then it turned red, there was some kind of chemical process going on.

As for re-x becoming more yellow, how do you know thats not n-oxide forming (and thus also a chemical process happening) at least in some cases?

And once again im not talking about a tan product turning more yellowish, im talking about some very white product turning very red. Im not saying it is for sure degradation of harmaline, but at least to me it seems to point towards it, maybe simple oxidation just like dmt n-oxide can be formed, maybe its something else, maybe its the degradation of some other impurity. Would be interesting to have more tests done.

Would be nice if others would try redissolving and re-evaporating with heat several times, harmalas, whether in salt form or freebase, and see what happens for others. Also would be interesting to know more about harmine/maline n-oxide, what does it look like. Maybe also trying to oxidize harmine/maline with hydrogen peroxide to see what happens?

I do understand that its possibly degradation, but I still lean more towardsfthe fat/dye side of the fence. I belive I read about someone running re-x on this red substance and retrieving more harmalas which makes me feel like its merely left over contaminants stuck in the end product rather than a byproduct of the re-x, and if it is oxidation then can it be from evaporation? I agree that it definitely requires more testing, but EtOH is what is called for in the Merck index, so why would they call for a solvent that would cause degradation of the product?

yeah but youre still talking about a different case.. you're saying that in one case you read about, someone re-x red stuff and came with more harmalas.. but how was this red stuff made in the first place? maybe in this case it was plant dyes and what not, but in my own case it was completely different: It was something already very white that became very red.

Just try to make it yourself.. and btw, I didnt use EtOH, I used IPA, for freebase harmalas. and the Merck talks about methanol and ethanol, I never tried with either. And in the case of ron who seems to have made harmala red with ethanol, it was with the hcl salt, and merck doesnt talk about crystalization of the hcl salt with EtOH..

Again, would be nice if someone else just tested to see if the same also happens with them. And hopefully one day a mass spec to analyze. Whatever the answer is, I would love to know

SWIM analyzed the red stuff by LC-MS. Will post results tomorrow or on weekend. its interesting but surprising as always.

Unfortunately I don't have any 99% IPA. And as far as what I can recall on that case I read it was relly pure rue extracted harmaline, re-x with EtOH left red behind which contained more harmaline that was recovered by successive re-x. I may be a little mixed up as I can't find it now. I think I should just order some IPA- or isin ISO-HEET 99%ipa?- and add that to the test.

Really look foward to the results.

I have no idea when my ethyl acetate will be in but I may just start my test with what I have now. Is there any other readily available solvents anyone would like me to add to my list? My goal now is merely to accumulate some solubility data and explore which solvents will produce this red dilemma.

I dont want to sidetrack the thread, but i have seen the term "slightly soluble" mentioned. So i thought this could come handy: http://www.pharminfotech.../pages/solubilities.html

It gives an arithmetic approximation of those terms so its slightly (1 in 150 parts ) better this way for people trying to assing a ballpark of how much solvent to try. Keep in mind also that solubility is a function of temperature, meaning that if you run experiments run them side by side in the same enviroment so your solvents have the same temperature.

Great link! Will come in handy. I have another 250g of rue to process and then I'm gonna get to it. Should have some results by the end of the month or the beginning of next month, depending on how much time I have. Its getting to holiday season so we'll see how it goes.