Easy way to very pure harmaloids

[whiterasta]

So I have played with this a bit and this method will give pure white freebase alkaloids from rue or caapi.
Extract material with acidic(any acid) alcohol(any light alky meth to iso)till it is only slightly flourescent under black light.
Boil down to heavy syrup and add a large portion of water. The tars and oils will separate and can then be filtered out till a tan clear liquid is obtained.
A large excess of NH3OH is added(clear cleaning ammonia) and immediate precipitation of the FB will result
Vacuum filter and wash with ammonia/water till wash is clear or decant and wash till clear
the FB at this point is light tan and clean enough to use as is.
The tan material can be salted with a slight excess of any acid and refiltered then rebased and washed for an eggshell white product
No measures are given as none are used and indeed none are really needed.
I only used a funnel, tissue paper plug and gravity, Vacuum would speed the process.
A small amount of CaOH added during primary filtration of the aqueous phase seems to clear the solution of tars and other colored contaminants quicker but is not necessary.

I have left this very general as it is quite striaght forward and self explanatory once one does it.

 

[lorax]

does the acidic alcohol need to be saturated? which PH should it have?

 

[lorax]

why use alcohol to do the pulls when the alkaloids are soluble in water? wouldn't it be more cost efficient to do the extraction with water? or does water also dissolve some stuff which one doesn't want which alcohol on the other hand doesnt pick up?

 

[endlessness]

I would like 69ron´s opinion on this.. he mentioned evaporating harmalas in alcohol leads to an inactive product called harmala red.. even if you dont evaporate all the way, still one could guess at least part of it is lost, if what ron says is true

btw, I know its straight forward and you dont want to give measurements, but I would love to know what ´excess´ ammonia means, more or less.. Is it like, a few drops, or many ml? would too much or too little be a problem?

thanks

 

[Infundibulum]

Harmaline is insoluble in ethanol and slightly soluble in hot ethanol. This is how I separate harmaline from harmine out of crude Manske-type peganum harmala extraction. Harmaline is almost pure white, and gives very nice romboidal crystals when crystallised out of boiling ethanol.

Harmine on the other hand is soluble in alcohol. Harmine is the "reduced" form of harmaline and it is synthesized (e.g. in TIHKAL) from reduction of harmaline chloride using strong acids. Again according to TIHKAL, this reaction takes place in boiling alcohol, out of which harmine chloride can also be precipitated as welloy needle-like crystals.

It is very unclear to me how ethanol can harm harmine and convert it to harmala red, especially when Shulgin's harmine synthesis involves plenty of ethanol. It has also been very difficult for me to find further info on harmala red and its structure.

For the moment I have incubated some amount of harmala alkaloids in boiling ethanol, got the precipitated white harmaline chloride out and waiting for the ethanol fraction (containing the dissolved harmine and possibly the presumptive harmala red byproduct?) to dry out. I am very curious to bioassaay it:wink:

 

[endlessness]

here´s ron´s quote

Yes, don't evaporate in alcohol. That is a known method of forming "harmala red" out of harmaline. There was a big industry based on making "harmala red", which was a dye commonly used for Persian carpets (now I think they use something cheaper). They made it by dissolving the alkaloids in alcohol and evaporating them in alcohol. If water is used, "harmala red" doesn't form. But if alcohol is used it does. Somehow, the water protects the harmaline from oxidizing into "harmala red", but alcohol encourages it to form. When harmaline hydrochloride is evaporated in water, it forms harmaline hydrochloride dihydrate, which is fairly stable, but when evaporated in alcohol it form harmaline hydrochloride anhydride which easily oxidizes to the inactive “harmala red”. Anyway, that's what I read in many different books on the subject, so I’d avoid using alcohol. SWIM has seen "harmala red" form right in front of his eyes when using alcohol. To avoid it, you need to evaporate the harmiline in alcohol in an atmosphere free of oxygen.

though indeed would be nice if alcohol could be used, also because one of SWIM´s idea was dissolving harmaline/mine in alcohol and soaking some herb with it, for transporting in nice unsuspected way, also for smoking and even ingesting.. Even though harmine/maline are not illegal where SWIM lives, he would just like to have a couple of tea bags where one is with spice and another with harmalas, and then one can smoke them, or ingest them.. the magic tea

and also SWIM just recently got 100gs of syrian rue and wants to try extracting it for the first time, and has 99,5 ethyl alcohol at home, also some ammonia hydroxide, and non-iodized salt, so basically everything is ready, just needs to know if this alcohol thing is indeed a problem or not

 

[Infundibulum]

Yup, I remember reading this part, but the activity and the structure of "harmala red", still remain obscure. It should be noted though that there's some logic to that thinking, simply because harmine SHOULD oxidise to something, (irrespective of whether it is active or not). As a matter of fact, the "pathway" from harmaline to THH is a reduction process

[EDIT 23/10/08: THIS INFO IS WRONG!
harmaline ----------> harmine -----------> tetrahydroharmine
................(reduction).............(reduction)

THIS IS THE RIGHT INFO]
harmine ----------> harmaline -----------> tetrahydroharmine
.............(reduction).............(reduction)


[EDIT 23/10/08: INCORRECT SPECULATION - see the right info above]
Which begs the question, if harmine does not oxidise to harmaline (just reverse the above pathway) what does it oxidise to? In Shulgin's TIHKAL notes the environment for conversion of harmaline to harmine was ethanol plus the presence of really strong and concentrated acids. Maybe this environment protected any newly formed harmine to oxidising to harmala red?

 

[69ron]

There is such little information about harmala red out there.

SWIM has seen it form after evaporating harmala alkaloids in 99% IPA.

Here's a picture of it:

Harmala Red Forming from Harmaline HCl

SWIM saw this "harmala red" junk form in a matter of minutes after evaporation in IPA at 150 C. These were hydrochloride salts.

SWIM never saw that happen after evaporating in water.

Heat may play a role in forming "harmala red". SWIM never tried evaporating in IPA without heat.

The structure of “harmala red” is not published anywhere. It is said to be inactive, but I really don’t know if it is or not.

This “harmala red” coloring is used in making old Persian carpets, and maybe it’s responsible for the “Magic Carpet” concept. Maybe it’s active, and maybe it soaks into your skin and makes you high if you sit on a red carpet nude. :lol:

I’m partially joking, and partially serious. Harmaline is known for giving people the feeling they are flying or moving if enough is taken. That’s exactly what a “Magic Carpet” is supposed to do. Maybe such a thing is real and caused by too much “harmala red” in the carpet?

Could harmala red be harmaline N-Oxide or harmine N-Oxide? Oxides are often reddish.

 

[fourthripley]

You've reminded me of an experiment I've had knocking around the back of my mind for some 10 years... make some sort of ointment from P.Harmala and apply to various parts of the body, insides of wrists, centre of forehead etc. Goes back to an interesting experience my wife and I had some years back when I had been playing with a largish quantity of seeds; grinding and making tea, not ingesting on that night, in a fairly confined space. Both experienced unique dream visions of a very satisfying and informative nature very much in the flavour of positive harmala and yage sans admixture reports. Wonder if skin administration maybe more promotes the visionary side of harmala? and wonder if in Indian culture there are maybe echoes of this?... the red forehead dot- is it called a bindi?- makes me wonder... One day I will try the experiment

 

[endlessness]

this has some interesting info about solubility and characteristics of different forms of harmaline.. It does mention harmala red but, of course, does not talk about it´s pharmacological activity

 

[69ron]

You've reminded me of an experiment I've had knocking around the back of my mind for some 10 years... make some sort of ointment from P.Harmala and apply to various parts of the body, insides of wrists, centre of forehead etc. Goes back to an interesting experience my wife and I had some years back when I had been playing with a largish quantity of seeds; grinding and making tea, not ingesting on that night, in a fairly confined space. Both experienced unique dream visions of a very satisfying and informative nature very much in the flavour of positive harmala and yage sans admixture reports. Wonder if skin administration maybe more promotes the visionary side of harmala? and wonder if in Indian culture there are maybe echoes of this?... the red forehead dot- is it called a bindi?- makes me wonder... One day I will try the experiment

Haha…I love the part about that red forehead dot from ancient Indian culture. Hmmm…putting oxidized red harmaline (harmala red) on the forehead might indeed cause an effect.

Hmmm…magic carpets made with dye from Peganum harmala…red dot on the forehead…hmmm…very interesting.

I’ll bet it does soak into your skin and is active that way.

SWIM has noticed that while working with Peganum harmala in the past that he could feel the effects of it. Simply powderizing the seeds was enough to get effects from it. Maybe it was landing on his skin and soaking in? Maybe he was breathing some of the dust in? He specifically tried not to breathe any in though.

 

[endlessness]

this mentions turkish red as identified with ´harmalol´, and then cites, as a source for this claim, a german paper from 1911 about the pharmacology of peganum harmala

does that make any sense?

 

[69ron]

SWIM tried harmalol before. It’s highly water soluble and not red. It was nice, sort of like psilocybin without the psychedelic effects. It was very different from the other harmala alkaloids. It’s highly water soluble and wouldn’t work as a dye.

There seems to be conflicting information on what chemical "harmala red" actually is. All the literature I’ve read seems to agree that it’s an oxidative reaction of some sort that makes it.

I think it’s actually harmaline N-Oxide. Oxides are usually reddish. It makes the most sense to me after reading all the sparse literature on the subject.

You can probably make it by dissolving harmaline HCl in hydrogen peroxide.

But then again, most N-Oxides are highly water soluble and “harmala red” is supposed to be poorly water soluble.

 

[prottel]

I remember when I used rue and over time it would become weaker. Then I would evaporate it, and let it stay in the oven for a while. Then it seemed to double in potency. Any reaction that could cause this?

 

[69ron]

I've heard that heat can decompose N-Oxides in some cases, so maybe the heat from the oven was converting "harmala red" (assuming it’s actually harmaline N-Oxide) back into harmaline?

N-Oxides are normally weaker than their parent compounds. Such is the case for DMT N-Oxide and Bufotenine N-Oxide.

 

[endlessness]

if harmala red is harmaline/harmine n-oxide, then the big question that we are left with is: Are these harmala n-oxides active? If so, at what doses, and are the effects different than their parent compound?

if the oxides are just or nearly as active, then alcohol evaporation wouldnot be a problem and SWIM´s ´double flavor magic tea´ is still a possibility

also, it might indeed be possible to convert it back to harmaline/harmine, just as dmt n-oxide is possible to do so, right?

 

[Infundibulum]

SWIM has "made" some harmala red by dissolving harmine in hot ethanol and let it at room temperature to slowly evaporate. This is different from 69ron's report in which case IPA was used and IPA was evaporated at 150 C.

SWIM's will bioassay at some point this week, both alone steadily increasing the dose, as well as in combination with spice. But these experiments will take some time... If no potency/activity is lost, then ethanol can be granted as a safe solvent for extraction:wink:

In the opposite side however it might be....Oh crap!

 

[lorax]

it would be really fantastic if we could nail this thing down at last. we need to write up a good tek for this! a friend has all this caapi vine lying around waiting to be extracted in a reasonable fashion. Maybe one could create a technique using only ethanol in the final(crystallizing) phase. it would be awesome if one wouldn't need to use ethanol all the way because it is a somewhat expensive solvent.

maybe one could use the manske method until one has a rather clean crude extract and then dissolve this in hot ethanol and let it cool until the alkaloids fall out of it.

the crystals i had made from evaporating ethanol were probably red because i used himalaya rock salt in the procedure, which is also kinda pinkish. i had evaporated the ethanol in the oven at 50°C.

what do you think? should i try redissolving my red crystals in hot ethanol and stick it in the fridge so the alkaloids will fall out clean without the red color? (altho i dont mind them being red.. looks kinda nice)

 

[endlessness]

it would be really fantastic if we could nail this thing down at last. we need to write up a good tek for this! a friend has all this caapi vine lying around waiting to be extracted in a reasonable fashion. Maybe one could create a technique using only ethanol in the final(crystallizing) phase. it would be awesome if one wouldn't need to use ethanol all the way because it is a somewhat expensive solvent.

maybe one could use the manske method until one has a rather clean crude extract and then dissolve this in hot ethanol and let it cool until the alkaloids fall out of it.

the crystals i had made from evaporating ethanol were probably red because i used himalaya rock salt in the procedure, which is also kinda pinkish. i had evaporated the ethanol in the oven at 50°C.

what do you think? should i try redissolving my red crystals in hot ethanol and stick it in the fridge so the alkaloids will fall out clean without the red color? (altho i dont mind them being red.. looks kinda nice)

AFAIK the alkaloids are way too soluble in alcohol to be freeze precipitated. The temperature of the freezer is not cold enough to make them crash out, so I think the only thing would be evaporation in the final step..

 

[Infundibulum]

AFAIK the alkaloids are way too soluble in alcohol to be freeze precipitated. The temperature of the freezer is not cold enough to make them crash out, so I think the only thing would be evaporation in the final step..

Yet I disagree! Harmaline chloride is insoluble in ethanol and very slightly soluble in hot alcohol. The picture below is harmala alkaloids from Manske precipitation mixed in ethanol, then incubated at 100 C for 10-15 min. One can see the harmaline falling on the bottom (left pic), it is so white one can assume very high purity. The top layer contains the dissolved harmine and other crap.

When this reddish supernatant was placed in the freezer overnight plenty of yellow needle-like crystals formed, i.e. a standard freeze precip of harmine-chloride from ethanol. This also gave very nice yellow crystals, again to be assumed of high purity (harmine-cl is yellow in colour). The rest of the reddish solution that did not produce any further precipitates was dried out (right pic). One can see some yellow harmine crystals forming, as well as the brownish impurity sitting on the sides of the. No signs of any harmala red from this very straightforward procedure so far; the brownish material as well as the yellow harmine are still soluble in water.