Rue to separated freebases with less fuss.

[Orion]

Here I've combined elements from very conveniently simplified approaches by Sakkadelic and Brennendes Wasser into one method. I've reworked a couple of details, removed some unnecessary steps and added quick and easy salt and optional separation stages. In my opinion this is an easy, quick way to separated Harmine and Harmaline freebase of reasonable purity and good yields without grinding of seeds or filtering and reducing of large volumes of water. No funnels, no cotton balls and no extra back and forth between acids and bases.

Materials:

• 100G of dry Syrian rue seeds
• Distilled vinegar or citric acid
• Sodium hydroxide (lye)
• Non-iodized salt (e.g. sea salt)
• Sodium bicarbonate (optional, for separation step)
• Sodium carbonate
• Coffee filters
• 2X 1L mason jars or pickle jars and one extra jar (for filters full of harmalas to sit in and rinse).
• A square of cloth such as a piece of an old T-shirt
• pH strips or meter (optional but handy)
• Turkey baster (optional)
• Large saucepan
• Water (clean tap water is fine).

​

Crude freebase extraction:

-Put 100g whole rue seeds in the pan with about 1.2L of water.
-Simmer for 10-15 minutes to drive off the chlorine (this makes PH testing more accurate).
-Add acid until pH 3 to 4. Vinegar works but can be driven off as it simmers. Citric is acid is ideal. 3 teaspoons is enough, more won't hurt.
-Boil for 3 hours and reduce to just about cover the seeds and decant into large mason jar through a piece of clean T-shirt cloth to trap larger particles.
-5 more 5 minute boils with only enough water to cover seeds. Adjusted pH with acid each time as needed.
-All boils should fit into 2 large mason jars (2/3rds full, leaving some room for lye solution).
-No reducing, no filtering. Base with lye solution. Clouding will form rapidly as the the harmala freebases, turning the solution milky.
-Alkaloids settle over a few hours. Add a small amount more lye solution. Stop if no more clouding occurs.
-Pour/ pipette (turkey baster) away as much water as you can without disturbing the settled freebase.
-Add fresh tap water and harmalas will settle again. Settling is faster each time. Repeat until the PH of the water is neutral. The color will be very faint.
-Collect and dry harmalas in coffee filter.

My yield was 7g of tan powder. Usually the yield would be about 5g with a lot of filtering in a normal extraction. From this current batch of seeds half of that would also be insoluble material which will be removed in the next step.

Manske:

-Dissolve freebase in 1 part distilled vinegar (roughly 75ml) in a pan on low heat, top up with 3 parts tap or distilled water (roughly 225ml).
-Filter solution through a coffee filter to catch dark insoluble material. From these seeds the insoluble material accounts for almost half of the crude freebase.
-Add filtered clear amber solution back into the pan and saturate with salt, stirring each spoonful until no more will dissolve at low heat (hot tea temp, below boiling).
-Pour solution into jar, leaving excess salt in pan. Rinse pan with tap water, fill and heat it. Sit the harmala jar this heat bath to slowly cool overnight.
-Next day, filter the crystals of Harmala Hcl and dry in the filter to obtain fine golden harmala HCl crystals.*

*Sakkadelic's drying tip: press the folded filter paper between paper towels to wick away excess water and salt. This is is useful if your desired product is the Harmala HCl as it is.



Separation of harmine and harmaline Freebase:

If you don't want to separate the freebases, simply skip ahead to adding sodium carbonate. This will force both alkaloids to crash out.
The following is a basic procedure but does not ensure full separation as tests have shown. See end of post for more info.


-Add crystals to pan and 200ml of tap or distilled water (pour through the filter which the crystals were recovered from to dissolve those stuck to the paper).
-Gently heat until everything is dissolved and filter into a jar through a coffee filter.
-Add 100ml of sodium bicarbonate solution (saturated at room temperature).
-Solution becomes slightly cloudy. Harmine begins to precipitate. More base solution can be added until no more precipitation is seen (it may take about 300ml total).
-Let solution settle for several hours then pour through coffee filter to collect harmine freebase.
-Rinse harmine 3x in the filter with cold tap water (as distilled water can be slightly acidic) to remove traces of sodium bicarbonate, then dry.
-Add sodium carbonate solution (saturated at room temperature) to the bicarb based tea. Pale harmaline freebase will crash out. Add more as needed (it may take 150ml this time).
-Let solution settle for several hours then pour through coffee filter to collect harmaline freebase.
-Rinse 3x in the filter with cold tap water then dry.

My yields: Harmine freebase: 1.9g. Harmaline freebase: 1.5g. Total 3.4% final yield after cleaning. Yield varies depending upon quality of seeds.



Notes:

I think a manske step is a good idea, and only one is necessary if everything was done correctly. Brennendes Wasser has shown some evidence that the insoluble remainder after adding acid is in fact just harmalas which won't dissolve for some unknown reason : Harmala extraction - unneccessary steps? . If this is the case, the dark insolubles could still reduce the effectiveness of a dose. In my opinion it does make sense to remove them. Further purification can be done to remove color, but if the product is as pure as the tests show then it's more about cosmetics and will have little to no effect on dosage. That said, you can manske and base to your heart's content. For simplicity I haven't included such steps here. See The Tao of Rue Extraction or Harmalas Extraction and Separation Guide for info about this.

If you want to grow nice crystals but don't want to go back and forth with manske and base steps, you can do it as part of this method as a freebase. Simply add your base solutions very slowly over a much longer period of time and you will see small crystal clusters develop on the sides of the jar and on the surface of the solution. This is easy for harmine as the pH does not increase too rapidly with sodium bicarbonate.



I don't recommend adding sodium bicarbonate powder or oversaturated warm bicarbonate solution to a cooler harmala solution, as I have seen this cause excess sodium bicarbonate to flocculate as spongey masses that seem to trap dissolved particles, apparently including harmaline. Doing this after all the harmine had been exhausted, I noticed a color change from pale orange to a lighter yellow. Adding sodium carbonate after filtering the bicarbonate globs away did not precipitate anything as it should have. After redissolving the mass in another jar of water and adding sodium carbonate, harmaline did immediately precipitate.

Some information on harmala separation methods:

Thread 'harmaloid purity'

Nov 2, 2010

Many people claim that they know what pure harmine and pure harmaline feel like. This is often used to claim that they therefore know what pure THH feels like. I want to point out that this is probably not true and that the vast majority of the time many SWIY's are simply eating mixtures with different ratios of harmine/harmaline (at least when using extracts from peganum harmala).

Using the NaCl + sodium carbonate precipitation method many try to take advantage of the pka difference between harmine and harmine to separate the 2. This separation is incomplete.

I post two example GC...

• burnt
• Replies: 21
• Forum: Harmalas

Post in thread 'Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols'

Oct 22, 2016

So this is how did a preliminary check of another paragraph in the paper: the pH-selective separation of harmine and harmaline.

In line with Van Der Sypt's experiment 2.3, I dissolved 6g of post-Manske (3 times) harmine+harmaline freebase in 35ml acetic acid 7% + 250ml of demineralized water. A little heating and some stirring quickly succeeded in dissolving all of it. After cooling, I added ammonia 12% dropwise under continuous stirring and observation of the solution's pH.

While adding the ammonia, the pH took off from around pH 4, rose quickly around pH 5 (typical titration-curve?)...

• An1cca

A harm-reduction approach to the isolation of harmine and its hydrogenated derivatives from Peganum Harmala seed in low-tech settings

ABSTRACT Background. Peganum Harmala (Syrian rue, Nitrariaceae) has a long and widespread history of ethnopharmacological use. Due to its rich and diverse alkaloid content, the traditional application of whole plant material or full alkaloid extract is inherently unspecific and therefore...

zenodo.org

 

[Sakkadelic]

Lovely

This in my opinion is the best route for clean harmalas. @blig-blug propsed that we re-write my tek and these are exactly the steps I proposed:

1- whole seeds, tea prep
2- basification and water washes. simplest way to get rid of most of the gunk
3- acidification and filtration
4- manske
5- basification and water washes
6a- drying and collection
6b- acidification, filtration and manske, collection and drying if HCl harmala is desired

A couple notes:

- I think the 7g you got at the beginning is very reasonable, I usually expect a 6% freebase yield, and since at that step no filtration was done yet a 7% crude freebase yield makes sense, but then what what happened? where did all the harmala go? You only got 3.4g combined freebase at the end, did you save some of the HCl crystals?

- for manske, especially if you're saturating the harmala solution with salt, I think it's good to try and pull away as much as possible the salty water before drying the xtals. Letting the wet harmala xtals dry on their own will result in a bit of salt contamination. I do that by gently pressing the folded filter between paper towels until no more water comes out and then let it dry. This is only relevant if the harmala HCl is the desired end product.

- I usually find it hard to collect the freebase with a coffee filter, is the filtered water completely clear?

Great tip for growing freebase xtals! i'll definitely try it next time.

 

[Orion]

Good to hear that one who inspired this approves .

I would say that the extra cleaning steps at the end should be considered optional if simplicity is what the tek is all about. Personally I don't think much cleanup is needed once the vast majority of the insoluble material is removed, in line with information Brennendes Wasser provided in the NMR results.

- I think the 7g you got at the beginning is very reasonable, I usually expect a 6% freebase yield, and since at that step no filtration was done yet a 7% crude freebase yield makes sense, but then what what happened? where did all the harmala go? You only got 3.4g combined freebase at the end, did you save some of the HCl crystals?

It's this batch of seeds which aren't actually that strong. Usually the yields are less to begin with and insoluble material accounts for about half of the initial yield. From these I usually get 5g crude with standard methods involving reducing, settling and filtering. This usually cleans up to 2.5g. From 7g the best possible yield therefore would be 3.5g. Here it was 3.4g, so this seems about right. I'll add a note about that in the post.

Good idea about the wicking moisture from the filter paper to remove more salt. It should speed up drying too. I'll add a note about this

- I usually find it hard to collect the freebase with a coffee filter, is the filtered water completely clear?

The usual color, but completely transparent. No cloudiness. I suppose not all coffee filters are made the same...

 

[conscious_wonderer]

Amazing write up. Thank you.

 

[doubledog]

Regarding separation of harmine and harmaline:
afaik separation depends more on exact pH value and is not so easily achievable. VDS paper claims that fraction separated by sodium bicarbonate still could contains some harmaline, eventhough it really is predominantly harmine.

 

[Orion]

True doubledog. From the Harmalas Extraction and Separation guide : 'pH 8,75, 92% of harmine present in rue will precipitate while only 8% of the harmaline present will precipitate'. So I suppose it's a case of precipitating as much harmine as you can with a tiny amount of harmaline, or precipitate less initially, but have more harmine in your harmaline after? Seems like there will be cross-contamination of a small percentage either way. Unless there is an exact pH which can guarantee perfect separation ?

 

[doubledog]

According to VDS paper, proper pH level for good separation have to be quite precisely measured (pH depression occurs when harmine precipitates), but is lower than pH 8.

 

[xa]

Sorry, in the first boiling step you use a t-shirt to wrap the seed or something like that ?

 

[Orion]

Sorry, in the first boiling step you use a t-shirt to wrap the seed or something like that ?

Clarified the wording there. I mean to say pour the boiled tea into the jar through the fabric laid across the top of the jar. This is mainly to trap seeds than anything, as all of the insoluble material will probably be removed after filtering the acid step. You might even get away with a tea strainer. I haven't tried it myself yet so I can't write it up.

Currently doing all of the same steps on 400g at once, with all weights and volumes scaled up 4x. 1L of water per 100g of seeds in the first boil this time. Even less water might work fine, but too much less and it could cause problems as the seeds swell up. We'll see once I finish up if the final result changes. This is from the same batch of seeds as before.

 

[Orion]

Looks like I have the same percentage of harmine. The harmaline is being filtered but looks quite clean as before. Larger quantities are still a hassle without vacuum filtration to speed things up and I feel it defeats the whole idea of this thread. For a simple extraction I think the weights and volumes in the original post work perfectly well.

 

[DetritusTheEgo]

Going to try this method in a few weeks with the amounts called out. Last time I did an extract for harmalas was about ten years ago with Harmalas Extraction and Separation Guide

 

[Transform]

Going to try this method in a few weeks with the amounts called out. Last time I did an extract for harmalas was about ten years ago with Harmalas Extraction and Separation Guide

Best of luck - be sure to report back with results!

 

[DetritusTheEgo]

Reading through to prepare and was curious on one part.

When basing with the lye solution in the first crude extract I am curious how much solution I should make? Should I aim for a pH when making it or maybe like a one part lye to three part distilled water ratio?

 

[Transform]

Reading through to prepare and was curious on one part.

When basing with the lye solution in the first crude extract I am curious how much solution I should make? Should I aim for a pH when making it or maybe like a one part lye to three part distilled water ratio?

You'll want a slight excess that corresponds to the 7g alkaloids per 100g of seeds, plus whatever excess of acid there might be. The 7g needs to be either converted into a molar equivalent and using that molar amount of sodium hydroxide [@ 40g/mol⁻¹], or multiplied by the MW ratio of sodium hydroxide to the average MW of harmine and harmaline, the latter of which is a more straightforward way of achieving the same thing.

Your suggested concentration of NaOH may seem reasonable enough, although you'll only be needing a couple of grams or so of lye, so a 1:25 solution may well prove to be easier to handle.

Have a go at the calculations if you like - remember to take the added acid into account as well - and I'll be happy to check your workings if necessary.

 

[DetritusTheEgo]

OP I don't want to hijack this thread with my extract questions / notes. Say the word and I'll make a separate thread and link to here.

You'll want a slight excess that corresponds to the 7g alkaloids per 100g of seeds, plus whatever excess of acid there might be. The 7g needs to be either converted into a molar equivalent and using that molar amount of sodium hydroxide [@ 40g/mol⁻¹], or multiplied by the MW ratio of sodium hydroxide to the average MW of harmine and harmaline, the latter of which is a more straightforward way of achieving the same thing.

Your suggested concentration of NaOH may seem reasonable enough, although you'll only be needing a couple of grams or so of lye, so a 1:25 solution may well prove to be easier to handle.

Have a go at the calculations if you like - remember to take the added acid into account as well - and I'll be happy to check your workings if necessary.

That was far more of an Organic chemistry reply than I was anticipating haha. I took one semester of chemistry in college decades ago. Didn't see MW of harmaline in the wiki but Harmine states 212.25. Seems like 2-7% is reasonable yield for syrian rue seeds but I have not really dug too much into it. I assume the "harmala alkaloid mass" assumed to be clean and fully extracted? OP had a 7g crude yield and I believe indicated his seeds were weak.

MW ratio = Average MW of harmine and harmaline / MW of NaOH
212.25/40.00 = 0.188

NaOH to use = Harmala alkaloid mass × MW ratio
2% alk assumption = 2g x 0.188 = 0.376g
4% alk assumption = 4g x 0.188 = 0.752g
7% alk assumption = 7g x 0.188 = 1.316g

My assumption is the amount of NaOH to account for the 3 pH solution, not sure if the seeds are basic and make the pH rise, with 1000 - 1500ml, also assuming based on volumes estimated here, is negligible for someone who doesn't have the ability to measure solids past one decimal point?

 

[Transform]

Didn't see MW of harmaline in the wiki but Harmine states 212.25.

Harmaline is merely dihydroharmine, the MW difference is largely insignificant.

not sure if the seeds are basic and make the pH rise

Harmalas will almost certainly be present as salt forms in the seeds.

My assumption is the amount of NaOH to account for the 3 pH solution, [...] with 1000 - 1500ml, also assuming based on volumes estimated here, is negligible for someone who doesn't have the ability to measure solids past one decimal point?

The goal of the exercise is to ensure that you have sufficient NaOH solution to both neutralise the pH 3 acidity and deprotonate the alkaloids rather than to prepare a precise amount of lye to exactly precipitate all the alkaloids and no more, so having an excess of lye solution will be fine since you'll be pipetting it in for the most part and observing progress by some means or other.

 

[DetritusTheEgo]

I felt like crap for a few weeks but still intending to work through this tek fully.

I am done with the first 100g whole seed crude extract and my yield was also in the 6-7g range minus whatever is in the coffee filter. So also in the 'weak' range of seeds but the ones I bought I'd say were priced accordingly. I did it with citric acid and distilled water down to 2.8pH and hot plate in the garage. The house was hot already and I did not want to bathe in the smell of the boiling seeds while I was already nauseated to the gills and headache ridden. I did mess up the three hour boil though. Be weary of how rapidly you are losing your liquid depending on your heat settings.

I had checked it every hour with a timer and between as I was walking around the house if I was out of bed. I checked at the two hour thirty min mark by chance and it reduced to the point where it wasn't covering the seeds any longer and I only recovered about 50-75ml of liquid from that boil. So I ended up doing a second 3 hour boil with the same volume / pH as the first boil and mentality that I didn't boil the harmalas away. I then did the five five minute boils after that. I will compare the yield of the first crude next time to see if my mistake caused anything of note yield wise after the first step.

Will work through the next two steps leisurely over the next week and post actual #'s / notes when done.

 

[conscious_wonderer]

I felt like crap for a few weeks but still intending to work through this tek fully.

I am done with the first 100g whole seed crude extract and my yield was also in the 6-7g range minus whatever is in the coffee filter. So also in the 'weak' range of seeds but the ones I bought I'd say were priced accordingly. I did it with citric acid and distilled water down to 2.8pH and hot plate in the garage. The house was hot already and I did not want to bathe in the smell of the boiling seeds while I was already nauseated to the gills and headache ridden. I did mess up the three hour boil though. Be weary of how rapidly you are losing your liquid depending on your heat settings.

I had checked it every hour with a timer and between as I was walking around the house if I was out of bed. I checked at the two hour thirty min mark by chance and it reduced to the point where it wasn't covering the seeds any longer and I only recovered about 50-75ml of liquid from that boil. So I ended up doing a second 3 hour boil with the same volume / pH as the first boil and mentality that I didn't boil the harmalas away. I then did the five five minute boils after that. I will compare the yield of the first crude next time to see if my mistake caused anything of note yield wise after the first step.

Will work through the next two steps leisurely over the next week and post actual #'s / notes when done.

I also ran out of water when I did the crude extract. I kept adding water to it.

 

[DetritusTheEgo]

So mine was an Arthur 'Two Sheds' Jackson kinda extract. I ran outta water on the first boil then my first manske solidified almost entirely on my first try as a result of not having everything fully dissolved. I've not done a manske, so wasn't sure really if any of the floaties were precipitation so entirely my fault. But I would say it was the perfect primer to re-familiarize myself with the mentality, zen, and patience of at home extracts. I have trichocereus that have been starving for months, hopefully potentiating, waiting for their Cielo fate.

I did a second manske by adding more salt saturated water, proportionate vinegar, and redissolved everything fully this time, which resulted in needle shaped crystals the morning after that second attempt. Those long beautiful crystals didn't last long though cause I did fold the coffee filter in half between paper towels and got as much water out via a good smashing to reduce salt contamination which I saw suggested by Sakkadelic. I had 6.3g crude from the first step going into the manske and the resulting dry manske product weighed 5.5g, so I lost .8g to insoluble material. I figured I would of lost a higher amount but I'm not complaining:



Obligatory harmine spiral:



My harmine has more color to it than OP but completely happy with it. Final result was 2.91g of harmine and .81g of harmaline so 3.72% combined:



I lost 1.78g from the manske to final harmine / harmaline separation, so I can only guess that I had salt contamination from my two stage manske failure. pH before washing the harmaline with tap water was 9.8 and left it for over sixteen hours to fully precipitate so not thinking I lost product to impatience. Welcome to feedback though.

One suggestion would be that I didn't look up the rough saturation point for water and salt before my first manske but did look up the saturation point of sodium bicarbonate and sodium carbonate in 100ml water. I would suggest doing that to get rough estimates of how much of each to shoot for instead of winging it and failing like I did with my initial manske. I also only had pink himalayan sea salt on hand. Next time I'll use a sea salt without random trace minerals just for peace of mind and the placebo of purity of final product when my chemistry skills are novice at best.

I had a calibrated pH meter, buchner funnel + hand pump, stirring hotplate, and a 25ml hand pippette at my disposal but this extract was much easier than my first extract of harmine / harmaline from Harmalas Extraction and Separation Guide which I can honestly admit I did not make it to the end due to repeating the steps 10-13 several times. I would say for sure friendly to those without any specific tooling.

Overall, thanks for the write-up and I'm glad I ran into it. Now to start my relationship with harmine / harmaline...

 

[Sakkadelic]

I had 6.3g crude from the first step going into the manske and the resulting dry manske product weighed 5.5g, so I lost .8g to insoluble material. I figured I would of lost a higher amount but I'm not complaining

I lost 1.78g from the manske to final harmine / harmaline separation, so I can only guess that I had salt contamination from my two stage manske failure.

There's a couple things you should take into account to have a bit better assessment of the efficiency of the steps. The freebase and the salt have different molecular weights so 1g of pure harmala HCl can be turned into 0.85g harmala freebase at most. and that there's always some losses with manske, I do not have an accurate number for this but I recall one knowledgeable member once mentioning 5%. if you try to basify the manske liquid to recover lost harmalas you might encounter the blobs, I never figured out what they were.