IMPROVED HARMALA ALKALOIDS EXTRACTION FROM SYRIAN RUE
WITH A/B CLEANUP TO HARMALINE FURMERATE:

by: director of sound 2010 www.mycotopia.net and www.dmt-nexus.me

First I would like to outline the procedure. it is rather simple and does not require the use of labratory equipment or expensive hard to get chemicals. most parts can be modified to work with what you have. lye can be substituted with potassium hydroxide and even sodium or calcium carbonate . the alcohols used in the extractions can be changed around, isopropyl (rubbing alcohol, ISO-HEET), methyl (HEET, laqure thinner), ethyl (everclear) will all work. i used britta filtered water. you can use bottled, distilled or whatever you have. tap water shouldn't hurt the yeild very much and rue seeds are cheap so you wont notice the .4g loss from using tap water when you are extracting 200g of seeds. the amounts of base used are crucial, too much and some of your alkaloids could be destroyed, too little and they wont crash out of solution. so as a rule of thumb it is a 4:10 ratio. if you have 10g of seeds use 4g of base, 100g seeds/40g base and so on. usually a 50% solution (allmost saturated) does the trick. just add untill the color changes. this might be a little more work than a manske extraction but you dont have to deal with salt contamination and the yields and results are clearly better. you get much cleaner crystals and not the 'sparkeling dirt' type stuff from a manske extraction. you will be able to eliminate all traces of Vasicine and Vasicinone, the more toxic alkaloids found in the seeds most likley responsable for nausia. they are also uterotoxic and a abortifacient so pregnant women or those planing on becoming pregnant cannot consume a full spectrum extract containing these (not that pregnant women should consume psychedelics and other drugs anyway IMO)



the first portion deals with extracting the major alkaloids from the seeds by changing them into a water soluable salt form instead of the tannate salt so they can be removed from the seeds by filtration later. for this you will use alcohol, vinegar, and a microwave (crock pot for larger ammounts). as with all extractions 3 is the magic number so you will boil the seeds with three fresh portions of vinegar alcohol. the ammount is not totally crucial as water can hold quite alot of harmala salts ( 5g/25ml). the second portion comes after you cool and filter the extracted harmal 'tea'. in this phase you will force the alkaloids out of the water by turniung them into a freebase leaving behind the tannins, chlorofil, sugars and most of the impurities you dont want in your final product. as you taise the pH you can do it in one shot (which i will do for ease of posting) or follow something allong the line of what the harmal master phlux does. ie the telepahtine tek., raise the pH to 7.7 and just harmine will precip, push it higher after filtering out the harmine and harmaline will precip. it also will greatly reduce the size of material you have to work from 1lb of seeds and a few gallons of 'tea' to what you can fit in a 500ml beaker (or 20oz bottle or two). for this you want to make the tea as polar as possable to reduce the ammount of alkaloids still stuck in the water. you will use lye to do this. and now the magic starts, as you add the lye nothing will happen at first. just give it a few good stirs and sit back, the color will change then crystals of the freebase harmala alkaloids will start to form. these you filter out and desolve in alcohol with vinegar to turn them back into a salt. evapuration yeilds good clean is crystals that are good as is. you could stop here if you like but i suggest proceding with the A/B purification. you will have a much cleaner and better looking product. this is where a little more science comes into play. you would scrape up the powder and re base it and extract the alkaloids with a non polar solvent like toluene, xylene or methylene chloride. you now left the salt and sodium acetate and other gunk that contaminated your crystals behind in the water solution. now you are at your last step. once you have you alkaloid laden solvent you simply shake it with an acidic solution. i use fumaric acid here as it would go better with your fumarate Spice you made and makes some beautiful crystals... there is a glitch here, fumaric acid does not dissolve well in water but dissolves in acetone and MEK, BUT the harmaline fumarate does not dissolve in acetone or MEK (if they are dry) so a mix has to be made. you would use 50% MEK/acetone 25% water and 25% alhohol for this. you may need to heat it to get a saturated solution and its okay of you put an excess of fumaric acid in because you will re-crystal your product.



now on to the seeds and the extraction. surian rue (Peganum Harmala) has been used for centuries and has many uses ranging from an admixture to Ayahausca and Yage to a middle eastern Spice . Ayurvedic medicine and a dye. witch craft dream enhancer to a noxcious weed as well as a psychedelic incense. a truely vercatile plant. all parts of syrian rue contain alkaloids but most are consentrated in the seeds which can contain up to 5-9%! That would mean there are 50-90g of alkaloids per 1 kilogram. about 5-6% of that is harmine and the rest harmaline. there is a way to compleatly eliminate the harmine and i will explane that later. ...



THE EXTRACTION OF HARMALA ALKALOIDS:

Chems: Materials:
syrian rue seeds suitable sized containers for mixing and storing fluids (glass or plastic as long as the toluene dosent dissolve it)
Water large plastic spoon for stirring
vinegar evap dishes
isopropyl alcohol (91% or better) cotton balls, green brillo/scouring pad and other filtering materials
xylene, toluene, or methylene chloride (DCM) 2 leter bottle for filtering
fumaric acid
Methyl ethyl ketone (MEK)
acetone
lye or potassium hydroxide


(note: put your seeds in the freezer the night before, they grind easier)

1.) Now that you have everthing togather and some time on your hands take the seeds out of the freezer and begin grinding. Leaves, stems ans sand/rocks could be mixed with your seeds, pick out the rocks and dirt clods, dont worry about the leaves and stems. You want to grind the seeds as fine as possable. The consistancy of fine coffee grinds with a few whole seeds will be fine. After you are done wheigh em out (or just guestimate if it said on the package) do this now because they soon will be a wet mush you cant weigh. I had a total of 557g (guess they gave me a little extra). once the seeds are ground 18oz. of very hot (not boiling) water is added per 500g to make a paste and start the saturation of the seeds so osmosis will work better later on when the vinegar is added. If the seeds are uniformly moist it will allow the solution to come to an equlibrium inside and outside the seeds faster once you add an acid/alcohol mix allowing a more efficent extraction.



557g syrian rue seeds


seeds in a bowl


the seed paste


2.) Add your alcohol/vinegar mix it is just a 50/50 mix of rubbing alcohol and distilled white vinegar with enough to cover the seeds with about 1 inch of fluid. My total was 500ml of each so 1L total solution. More may need to be added as the seeds absorb the mix. If it is a smaller ammount of seeds you can use microwave safe dishes in the microwave. If you do that microwave in 45 sec intervals untill it is boiling and let it cool before squeezing out the 'tea'. For larger ammounts use a crock pot. Just load up the seed paste add vinegar/alcohol and set to high. Stir it every couple of minutes untill it starts to simmer. Then stir it a bit more but keep it simmering for 30 min. Let it cool and squeeze out the tea. For both methods do this 3 times, the exception is the last (third) acid pull mix your vinegar/alcohol mix 50/50 with water or use 50/50 water and vinegar. when harmine is heated in an alcoholic solution of acetic acid it is hydrolyzed into harmaline. so all this tea you made contains cheifly harmaline, some organic dyes and tannins as well as several other slightly toxic alkaloids (though in the .05% range, ie a few hunderd ppm) now that you have all 3 extractions, combine them and filter untill clear or let sit over night for plant particals and fine tannins to fall out. The total volume should be just over 3L. Filtering will still have to be done after straining out the seeds with an old shirt. The best final filter i found was a cotton ball stuffed in the neck of a 2 leter with holes drilled in the cap. It takes a while so vacuum filtration is the best. A hand vacuum pump can be had at amercian science and surplus for under $20. All in all you want the 'tea' to be crystal clear. I layered in the neck of a 2L first the cotton ball wetted with a little of the solution then 1/2 inch of sand followed by the green scouring pad material cut to size. I followed by pouring through a perminant coffee filter fitted with a activated charcoal filter to catch any sand that got through.


making the tea with 1000ml vinegar/isporopal


total acid pulls


FREEBASING THE ALKALOIDS:


3.) Now that you have your crystal clear 'tea' you make the alks crash out by adding the lye solution. Mix up your lye solution in about 3 cups of ice cold water and wait for it to cool before adding to the 'tea'. Stir it up real good. You will see a slight color change from a yellowish borwn to a darker chocolate brown. Its clear for the moment but soon it will start to cloud up. Over the next few minutes you can watch freebase harmaline crystals form and sink to the bottom. I ended up using 200ml of a 50% NaOH solution. A few more ml of base was added and stired up again to maximize the base to see if anythine else precips out. Once it has all settled decant what you can and filter the rest. For this i used cotton ball stuffed in the neck of a coke bottle and let it drip dry overnight before proceding to the next step.


after the lye addition


given time freebase xtals form


and start to fall out of solution


then finally settle into a layer on the bttom


then you just decant and filter the muck at the bottom to get this!


4.) Suspend your freebase harmaline 'muck' in alcohol (about 20ml/1 heaping tbsp muck) the 'muck' will not dissolve in the alcohol you need to salt it to get it to dissolve so begin adding vinegar untill all the solids are dissolved. The evap goes faster if you use alcohol, mine had straight vinegar added to it. Keep adding untill nothing else dissolves. Not everything will dissolve, There may still be bits of plant material or other gunk you dont want. Filter it one more time through a cotton ball and pour it in a dish to evap. Before you filter you could add activated charcoal if you want to clean it up a bit more if you are going to skip the A/B cleanup. Use a course charcoal, the stuff in say GNC or store brand activated charcoal pills is way fine and goes through a cotton ball if you use any pressure or vacuum, drip only... I added 2.6g of this GNC charcoal and found out the hard way. If you use something fine let it settle overnight and decant/syphon off the charcoal and sediment before filtering. It ended up taking me several hours to filter the solution but I was rewarded wath a crystal clear dark neon yellow solution. The filter cake was washed with a little hot vinegar to get out the last little bits of harmaline before it got discarded. if you evap from an alcohol solution you can get flaky crystals but if it is evaped from just vinegar like i did you will get a thick syrup. a small ammount of salt was added (10g) and shaken causing the entire 250ml or so to solidify into one crystaline mass. the excess vinegar was removed by vacuum filtration. an aditional clean up can be preformed if you want clean acetate salts for smoking or if you want clean freebase. after the evap by taking the thick yellow/red syrup/crystals (no not harmaline red...) and re basing them followed by 3 washes with a weak sodium carbonate (ph5) solution. you can then dissolve the freebase in anhydrous acetone to remove the leftover NaCO3 salt and lye. for the clean acetate salts you would suspend in alcohol again and add vinegar dropwise untill a semi clear solution was acheaved, filter and rex from a hot anhydrous alcohol.

the acetate mother liquor all dissolved in the bottle with just vinegar and no alcohol.


in the evap dish... took a long time to evap to the syrup...


but ended up with 47g total acetate salts.


A/B CLEANUP / EXTRACTION:

5.) With your scraped up harmaline acetate salts in hand, weigh them out and jot that down somewhere. Set some aside as the acetate salts can be smoked but the furmerate cannot. The fumerate salt decomposes into freebase harmaline and maleic anhydride when heated which is about as corrosive as phosphoric acid and you dont want that going into your lungs... The acetate salt on the other hand is quite smooth with no burn and barley any taste at all. Dissolve the salts in the minimum ammount of hot abs. isopropal alcohol ( anhydrous, 91% or better). Any left over salts will not dissolve and can be filtered out. Charge your flask with this solution and add acetone some to not quite double the solution but mabey 25-30% more. This will keep the freebase dissolved rather than letting it crash out when you add the lye. Once again mix up your lye solution but chill it in the freezer before adding to your solution. You will see a color change again, let it warm to room temp and swirl it around every now ans then untill no more color change happens and then then put in the freezer overnight. When you look at it in the morning there will be a layer of brown 'oil' on the top of a clear milky liquid. Add your xylene, toluene or methylene chloride now (or a mix there of) . It will pull out the harmaline freebase and leave behing all the salts and the last of the gunk that was in the alkaloids. Pull this off 3 times with just a little xylene/toluene/methylene chloride. you dont need to use half a gallon, as you can see i am working the extract from over 500g of seeds in a 500ml flask. You just got rid of the last of the salts and inert matter that was in your extract. i did an additional wash with a consentrated NaOH and NaCO3 solution (20g of each in 100ml)


first pull with 100ml of solvent and 150ml lye solution plus the acetone & MEK to keep the freebase dissolved.


second pull.


combined pulls.


washing with consentrated lye/soduum carbonate solution


6.) Now take some hot isopropyl alcohol and dissolve as much fumaric acid in it as possable. Add 250ml of this to your xylene/toluene and shake it up (less for smaller ammounts of seeds of course). It should become slightly cloudy and start to change dark yellow-redish. The yellow color will go into the bottom layer, your furmaric acid/alkaloid solution. Pull that off and add 1/4 that ammount fresh fumaric acid solution and shake again. It will be less yellow or not yellow at all your solvent should now be clear to slightly yellow again. Now just evap what you have. It should go real quick in front of a fan as the alcohol evaps quick and pull water with them. In this step you left behind the oily toxic alkaloids that cause the nausia and gastrointestional problems encountered when eating seeds or a tincture.


salting with FASI.


RE-CRYSTAL:

7.) As you can see the crystals fron the last evap dont look too good, chunky, feathery, different shades of yellow, brown and red-orange with a few needles here and there, thats because there is a bit of fumaric acid and sodium fumarate in there contaminating your harmaline. scrape everthing up and again dissolve in the absolute minimum of cold abs. isopropyl alcohol (91% or better). Filter out the stuff that dosent dissolve and put back in a clean evap tray. An additional recrystal can be done from pure water to eliminate the very last little bits of furmeric acid and other gunk. You should now have these nice super pure needle like amber colored crystals of harmaline furmerate. Be careful with these. Fast or stick to the diet when using MAOI's. and as allways be responsable and dont over do it. MAOI's can make yout usual dose of mushrooms seem like you just ate five times the ammount....


the evap tray (note: this is only 50ml of the total 500ml evaped right now)


close up of xtal formations


another close up

(more pics to be posted when the evap and rex are done)


sneak peak of harmaline fumarate crystalized from water

http://forums.mycotopia....yahuasc...trictions.html (MAOI FAQ - DIETARY & DRUG INTERACTIONS / RESTRICTIONS) MAOI dietary restrictions.

http://forums.mycotopia....otanica...age-guide.html (DMT Oral Dosage Guide!!) DMT/Spice oral dosage guide.


http://forums.mycotopia....line-tek.html#post911282

Wow this is incredible; very professionally done. SWIM will bee trying this out soon.

very very super sexy tek and glassware - nice one dos.

Thanks

Its probably the nicest Harmala tek i have seen until now.

------
Now , could you be more specific about part 4.



So basically you need to put your X-tals in water(or alcohol), make another solution with the same amount of base used as in the 3rd step , add it to the water or alcohol ,wait until all precipitates and filter ? If yes, than what would be the point of evaporating the vinegar or vinegar/alcohol mother solution ?wouldn't it be simpler to re base it in the original mother solution ?




ok ,so SWIY crashes it with salt but if the salt has dissolved completely, the next alcohol wash in step 5 will clean it up ? and from there he filters through a filter and keeps
the filtrates right? Thats because he only wants an acetate.

on step 4 i must have for got to edit that out, i pre-typed the tek before i preformed the extraction, the filtered freebase gets washed and re-filtered with a sodium carbonate solution to remove the last little bits of gunk from the original tea it was based from. then the washed freebase is added to alcohol and vinegar added until it all dissolves. i added strait to vinegar with no alcohol and only got a syrup this time. once the acetate mother liquor is evaped down to a syrup the salt is added to cause instant precipitation. and yes when you dissolve the acetates in isopropyl as long as it is 91% or better the salt wont dissolve but the acetates will. when you evap the de-salted alcohol solution you can get a cleaner product to use as an acetate salt if you want to smoke some. i proceded past that and used the still salted acetates through step 5 as the salt wont be pulled into the solvent and will make the aqueous layer more polar to push out the alks better. so disregard the 'additional cleanup/rebasing' if all you want is harmaline fumarate in the end. if you want some real clean acetate salts for smoking i would preform the additional on a portion for that. the reason for doing it twice is because when you rebase form a consentrated solution it is easier to control the ph and use less base by adding it little by little, this will also facilitate the removal of any leftover Vasicine and Vasicinone that is in there. they will not precip under weak basic conditions but will at the higher ph needed to precip ate freebase from a large ammount of solution.

Crystal clear like water or crystal clear like that you can see perfectly through the solution ?


Also,isn't the smokeable product supposed to be freebase and the one taken orally an acetate ?

Or is the acetate capable of being smoked and taken orally ?

What is the shelf life of the one that is taken orally ? If one does not want to go make the fumarate.

'crystal clear', i filtered out all but the smallest particulates and tannins that were in the original tea. so i could see through. it was not 'clear' as in like water it was still the same color as the origional tea just with no plant material in it anymore, kinda like tea or coffee, they are dark colored but you can still see through them. yes the acetate can be smoked and taken orally, all harmaline salts are very stable over time. i had some acetate salts that were about a year and a half old and still had the same effectiveness as the day they were made. i am unsure how stable the freebase is over time, generally freebases either oxidize or form a carbonate on exposure to air and moisture. i have allways salted mine every time so i cant say from first hand account how stable freebases are. though i have heard of people using freebase harmalas over a year old.

when you say " the entire 250 ml or so ", you mean that you added 250ml water or vinegar to your syrup ? also the salt would have to be dissolved in a hot water solution before
adding it to make the .hcl ?


Also as you stated that the muck will not dissolve in alcohol; then why not just mix properly the muck with alcohol,wait,decant and do this 2-3 times or until alchohol is much clearer
and then add vinegar ,filter,evap....... etc ?

i had 250ml of syrup total that the salt was added to. the salt was not dissolved in water it was added strait to the flask, agitation in an attempt to dissolve the salt caused the crystalization. it does not make a HCL it just makes the water/vinegar still contained in the syrup so polar that it can no longer keep the harmaline acetate dissolved. after filtration there was only 37ml of slightly yellow liquid containing barely any harmaline acetate and mostly salt. as for washing freebase with alcohol, you could do that because the freebase is not too soluable in alcohol but some (very small ammounts) will still dissolve so you would loose yields and i do not belive it would become clear. the purpose of the alcohol is to expedite evapuration of the liquid containing the acetate salts.

part 4.
how much vinegar did SWIY use when dissolving the muck for your tek ? 750ml more ? Does it dissolve like if you would dissolve sugar in water ? or does it all suspends itself in
the vinegar and falls ? Swim dreamed that he added 20ml alkohol/tbsp muck, then added 500ml vinegar and practically nothing dissolved,the muck fell to the bottom,just like when he added it to the alcohol before and some of the muck was still suspended in the red vinegar layer.Swim dreamed that he would add more vinegar and that heating the solution would dissolve everything.
Will it work?







Ok so your syrup was pure vinegar + your freebase right ? If someone was to work with dried stuff evaped from alcohol then how much vinegar would he have to use ? aprox. the same amount
you used ?

i added slightly under 600ml vinegar to the freebase muck. as it all reacts to form harmaline acetate with the vinegar it will begin to dissolve. it isn't instant, for the most part it will take a few minutes of shaking and if there is still stuff floating around add more vinegar and shake until it clears up, heating could speed it up but it really dosent take that long. if you cant get it clear you didnt filter enough but thats okay because you can filter it now. there would be no such thing as vinegar + freebase, all freebase would be converted to the acetate salt given enough vinegar to react with. if one were to start with any freebase wet, dry or otherwise the vinegar would stay the same. you dont need to add any vinegar after you precip it with salt or evap the original mother liquor from the freebase/alcohol/vinegar mix. you would go to step 5 from there.

Ok so in step 4 , you did not evap your vinegar fully , you only evaped until it was that 250ml and then you added the salt right?

---

Swim dreamt that while evaping the vinegar on a small heat, black tar would start to appear everywhere .what was that black tar ?

---

Also how would you isolate harmaline from your acetate salt ? would you have to freebase it and then isolate it ?

are you suggesting putting ipa into a microwave? or the seeds?

incredible write up, very very nicely done. well written, on point.

-gir

i have done many smaller 100g extractions in the microwave... no problems if you only nuke for short intervals. tops i had to nuke twice for 45 sec. each to get the IPA to its boiling point and if you think about it since it is a 50/50 mix of 70% ipa and vinegar its only 35% alcohol or less in the solution. most microwaves have a ventalation fan that will clear away vapors, so as long as you dont have any metal objects in the microwave to cause sparks you will be fine.

---------------- yep just got tired of waiting forever for the vinegar solution to evap. stopped at 250ml because it would fit in my glassware with room to play. secondly i knew at that consentration most if not all of the harmaline acetate would precip out when salt was added.



--------------------- the black tar could be some plant sugars or some other contam, i really cant tell you off hand what it might be because i have never seen that happen before, the highest temps i have used while evaping or consentrating solutions is 50*C or about 125*F. if you went above that it could be a decomposition product.



you wouldn't be isolating the harmaline FROM the acetate salt, it is an acetate salt as in harmaline acetate. the acetate ion is chemically bonded to the harmaline forming a salt. what ever left over NaOH (lye) that was trapped in the harmaline freebase from your origional tea you added the lye to will react with the vinegar forming sodium acetate. that can be removed by compleatly drying the harmaline acetate salts and dissolving the powder in an anhydrous alcohol (or at least 91%), the sodium acetate wont dissolve but the harmaline acetate will so after you stir/shake for a while and everything has dissolved but a little bit of a whiteish sediment/powder filter it and save the filtrate (liquid) the powder trapped in the filter is the sodium acetate. this will also remove any salt in there if you used salt to precipitate your harmaline aceate. if you wanted just freebase harmaline you would dissolve the harmaline acetate in water and basify it with a consentrated lye solution to precipitate the freebase harmaline. after you filter out the freebase, dry it (bone dry) and dissolve in anhydrous acetone or MEK. the freebase will dissolve but the excess lye will not. you will be able to filter it out and evap the acetone or MEK to get some fairly clean freebase harmaline.

Sounds like recipe for disaster! Maybe you personally didnt get it to catch on fire or explode yet, but to put the idea of micrwaving flamable solvents in a tek and spread it around is quite irresponsible, dont you think?

If you think of the responsibility you have when spreading information, and of all the people that might read this and put it in practice in their unique environments, chemicals and equipment, and with all the risks it brings, when you say such things you should post a HUGE GIANT RED FLASHING disclaimer, in the very least, or better, I think you shouldnt recommend this AT ALL!!

Here's a paper on microwave and flammable solvents.



so please, for the safety of everybody who might read your tek and this thread, remove that recommendation from your post.

I wouldn't suggest putting anything with a high vapor pressure (evaps quickly) in the microwave. IPA is both volatile and flammable.

Thank you both Endless and Benzyme.

Please read the Health and Safety Guidelines.



Not trying to bash you.. but other peoples microwaves are stronger, and probably will ignite.. so...just take the time and get some really nice boiling oil or water, they get really hot too ya know...

-gir

Whats the final freebase yields from this? Looks awesome by the way

i think the total freebase yield was something like 52g wet, i didnt dry it out before salting but it probally would have ended up in the area of 48-50g dry so close to 5% alkaloids in the seeds i got on ebay.