A new level of harmala purity with this extraction

[whiterasta]

Material is exhaustively extracted with acidified alcohol, I used food grade phosphoric.
the alcohol is driven off and the extract redisolved in water and filtered till clear
this should give a pale red liquid with rue and leave a greasy red dye in the filter
Caapi gives a clear yellow liquid after filteration with a dark brown greasy residue.
At this point the extractions look very with caapi being brown instead of red
the solution is basified with Ammonia and the fine dark FB settled and the liquid decanted.
Add more water to the FB and repeat settling and decantation till clear water is all you get.We are washing the solids and discarding the liquids
A buchner with a very fine filter would do this much more quickly.
add FB to excess phosphoric solution for a red acidic salt
neutralize to Ph 6 with CaOH( binds to coloring substances and impurities) and filter to near clear or very pale yellow.
Dry salt, chop fine and quckly wash with 95% EtOH for greyish white crystals.

This method using phosphoric acid gives a highly separable salt of harmaline (almost insoluble in concentrated solutions) which will precipitate as needles far sooner than harmine and can easily be filtered off for separating the alkaloids. I did not take photos as I wuz 'sperimentin' but I will repeat to demonstrate the benefits of this method over repeated Manske extractions to produce a very pure product which compares to commercial harmala alkaloids in appearance and purity. The harmaline "crash out" of this method alone is highly desirable, but the end purity is what separates this method from the Manske method and others.
WR
PS Note the only solvents are water and alcohol.The acid is flexible but I like the phosphate salts. The end product can be insufflated with little discomfort.
Here are some pics of the finished product one is the washed FB in water the other is the dry FB. As you can see it is as clean or even cleaner than many commercial products

Contact Support

 

[acolon_5]

Wow, that is beautiful!

Could you write up a step by step tek for some of us less chemically inclined kitchen chemists?

add FB to excess phosphoric solution for a red acidic salt
neutralize to Ph 6 with CaOH( binds to coloring substances and impurities) and filter to near clear or very pale yellow.
Dry salt, chop fine and quckly wash with 95% EtOH for greyish white crystals

Is the end product Harmine or Harmaline and how are both seperated and collected?

Also for Caapi will the tetrahydroharmine also be extracted and where will it end up?

 

[Entropymancer]

At pH 6, the harmine will be predominantly in the acid form, where it's water-soluble, while the harmaline will be predominantly in the freebase form, and should be relatively insoluble in water (I couldn't find a pKa for tetrahydroharmine). So it seems like this process would seperate the two, at least to some degree. I'm not sure I understand this part though:

filter to near clear or very pale yellow.
Dry salt, chop fine and quckly wash with 95% EtOH for greyish white crystals

It sounds like we keep the filtered precipitate at this point? But a harmala salt (which is the intended product as I understand it) should be water-soluble, and end up in the filtrate. And of course if we evaporate the filtrate, there's all the nonvolatile phosphoric acid hanging around in the product when it dries.

 

[acolon_5]

Right? I thought that harmine was much gentler and the preferred product over harmaline.

If, after we removed the precipiate (harmaline) and then basified further we should end up with mainly harmine crashing out... yes?

 

[Entropymancer]

Yeah, that sounds right. And since the material would be pretty pure, it'd be a simple matter of weighing it to calculate the proper amount of acid to salt the material out.

SWIM may have to order some rue seeds to play with. He did a harmala alkaloid extraction (a la manske) a couple years ago for fun but never ended up trying any of the product. SWIM is definitely interested in an effective extraction that doesn't seem as crude as the salt method.

(And welcome to the Nexus, whiterasta. Your posts here and on other boards are quite informative)

 

[whiterasta]

This is a first draft and I will write up a quantitative tek soon This tek simply sprung from clearing an Aya brew only just a couple weeks ago and I am still refining the process. This all can be done with vinegar, pickling lime and ammonia and tissue paper filtering. so it is very kitchen friendly and food grade pure.I am beat from work so the final draft may be a few days off but I will post when it is finished. I am just giving out the early results as they were quite spectacular considering the overall simplicity.

 

[tarutaru]

Anyone have an idea about how much acid you can use for this and does muriatic work?

tt

 

[acolon_5]

It sounds like an A/B extraction...HCL (muriatic acid) will work fine I assume, pH does not need to be too low I would imagine, extraction can take place at anything below neutral.

I would just bring it down to about a pH of 3. That seems like a decent pH for most plant extractions.

 

[Entropymancer]

So I've got a question: Why does the Manske extraction even exist? This works so much better, to extract, precipitate freebases as an off-white material, then proceed to clean up from there.

I'm currently in the process of doing a harmala extraction. Pulverized the seeds in a grinder and soaked them overnight, then boiled them in three fairly minimal volumes of water, acidified to pH 5.5 with citric acid (just a teensy pinch). I mixed my extraction with my saturated salt solution and put it in the fridge, on ice. No precipitate was seen to form.

So I figured, Ok, I'll just boil it down some and try again. Just as it was coming up to temperature, I figured, "Hey , what harm could it do to neutralize the solution before this next precipitation attempt. So I stirred a gentle dusting of calcium carbonate into the solution. Around the time it reached pH 6.5 or 7, clouds of lighter material could be seen billowing from the bottom as I stirred. The mixture was transferred back into the precipitation vessel and popped in the fridge. Within an hour, a thick layer of bright off-white freebase could be seen coating the bottom of the vessel.

I'm currently in the process of cleaning the freebase with volumes of water, as with Rasta's method, only I'm adding some salt and a very little calcium carbonate to the water. It looks to be going very well.

So what I'm wondering is: why did Manske go through the messy business of salt-precipitating the crude extract? Why not precipitate the freebases, wash with water, then seperate the harmine from the harmaline with salt precipitation? It's not like Manske didn't know what he was doing. I'm just kind of baffled by this.

 

[Entropymancer]

Wow. I'm impressed with how much of an improvement this is over the classic Manske extraction. And it's definitely not necessary to use ammonia; I used calcium carbonate with the same degree of success. If I'd had phosphoric acid, I'd have tried that, but my local brewshop was out. Instead I used citric acid; I wasn't able to seperate the harmine and harmaline this way, but I'm nonetheless more than satisfied with the results.

Sorry I can't give my yield as I freehanded the whole process. I'll see what I can do about aquiring a scale before processing the rest of this batch of Rue.

The product is very nearly white, with the slightest hint of pink or brown. Alas I have no camera, but the material looks every bit as nice as that posted by WhiteRasta. I can't begin to imagine why Manske didn't prefer precipitation by neutralization.

 

[lorax]

whats up with that tek man? did you ever get to rewrite it to a step by step tek for us nonchemists? i would like to try this tek on the weekend.

 

[Psychologic]

Would this stuff work?
pH Down 81% Phosphoric Acid


Anything I've found with a higher purity seems highly regulated.

 

[acolon_5]

Would this stuff work?
pH Down 81% Phosphoric Acid


Anything I've found with a higher purity seems highly regulated.

Sure would.

 

[kaos.underwave]

are you sure? I mean thats the stuff SWIM uses in his hydro res for the plants...sure theres just p acid in there? if so, then great

 

[kaos.underwave]

great work by the way, wr

 

[acolon_5]

No, I'm not positive, but my guess is that it will be fine. A few drops is all you need and any impurities in there would be SO small that it shouldn't present a problem.

If you are super concerened about it Beer beer and more beer has 10% Food Grade Phosphoric Acid.

I suspect though that what you have should be more than adequate.

 

[acolon_5]

whats up with that tek man? did you ever get to rewrite it to a step by step tek for us nonchemists? i would like to try this tek on the weekend.

Well it just sounds like an A/B extraction....

1) make slightly acidic water (I imagine most acids will work just fine, from HCL to citric)
2) cook seeds in acidic water x2
3) add small amounts of basified water until precipitate forms (I imagine that most bases will work fine including lye)
4) collect precipitate and dry
5) purify as needed via washes and/or recrystalization


I think I am starting to hate Manske....this is so much simplier and there is no need to get all that salt out of the final product. What was he thinking?

 

[Psychologic]

whats up with that tek man? did you ever get to rewrite it to a step by step tek for us nonchemists? i would like to try this tek on the weekend.

Well it just sounds like an A/B extraction....

1) make slightly acidic water (I imagine most acids will work just fine, from HCL to citric)
2) cook seeds in acidic water x2
3) add small amounts of basified water until precipitate forms (I imagine that most bases will work fine including lye)
4) collect precipitate and dry
5) purify as needed via washes and/or recrystalization


I think I am starting to hate Manske....this is so much simplier and there is no need to get all that salt out of the final product. What was he thinking?

If I'm reading the original post correctly, it is slightly different than what you listed. Tell me if I'm misunderstanding any of it.

1) Extract with acidified ethanol (pH?), evaporate alcohol, then redissolve dried extract in water (I guess the alcohol doesn't dissolve some impurities that water would?)

2) Filter solids out of water

3) Basify water with Ammonia to precip freebase. Decant liquid then repeat until resulting water is clear. Keep solids, discard liquids.

This is all the same as what you listed with the exception of the ethanol step, then he goes further to convert the freebase into a salt.

4) Add freebase to acidified water (pH?) and then neutralize pH to 6 and filter out solids.

5) Keep either the liquid or the precipitates (???).

6) Wash extract with ethanol.



My questions are:

1. When neutralizing pH in step 4, are the harmala salts still in solution or do they precipitate out and leave the impurities in solution?
2. What pH is needed in the acidic solutions?



This is just what I gather from reading the post, and I am certainly not confident in my interpretation. The purity of the resulting harmala salts are enticing, but I have not yet tried this method.

 

[acolon_5]

whats up with that tek man? did you ever get to rewrite it to a step by step tek for us nonchemists? i would like to try this tek on the weekend.

Well it just sounds like an A/B extraction....

1) make slightly acidic water (I imagine most acids will work just fine, from HCL to citric)
2) cook seeds in acidic water x2
3) add small amounts of basified water until precipitate forms (I imagine that most bases will work fine including lye)
4) collect precipitate and dry
5) purify as needed via washes and/or recrystalization


I think I am starting to hate Manske....this is so much simplier and there is no need to get all that salt out of the final product. What was he thinking?

If I'm reading the original post correctly, it is slightly different than what you listed. Tell me if I'm misunderstanding any of it.

1) Extract with acidified ethanol (pH?), evaporate alcohol, then redissolve dried extract in water (I guess the alcohol doesn't dissolve some impurities that water would?)

2) Filter solids out of water

3) Basify water with Ammonia to precip freebase. Decant liquid then repeat until resulting water is clear. Keep solids, discard liquids.

This is all the same as what you listed with the exception of the ethanol step, then he goes further to convert the freebase into a salt.

4) Add freebase to acidified water (pH?) and then neutralize pH to 6 and filter out solids.

5) Keep either the liquid or the precipitates (???).

6) Wash extract with ethanol.



My questions are:

1. When neutralizing pH in step 4, are the harmala salts still in solution or do they precipitate out and leave the impurities in solution?
2. What pH is needed in the acidic solutions?



This is just what I gather from reading the post, and I am certainly not confident in my interpretation. The purity of the resulting harmala salts are enticing, but I have not yet tried this method.

Quite right! Thank you. I completely missed the alcohol step and wash at the end. I have read about people not acidifing when they do an initial water extraction without any problems so I imagine that the pH does not need to be too low. I believe entropymancer said his pH was 5.5 using citric acid. I don't think it would hurt to go lower, but I doubt it would help.

The harmala salts are still in solution in step 4, adding the base will make them crash out as a solid from the basified solution.

 

[christoadfur]

So SWIM had an experiment going in which he;

-Ground 100g of syrian rue seeds

-Boiled in about 600ml of distilled water acidified probably too low (2.7) with citric acid for 40 min

-Strained through a t-shirt

-Process was repeated and extractions were combined

-Super saturated saline solution was allowed to cool to around room temp and excess allowed to precipitate out while aqueous solution was reduced to 400ml

-Aqueous solution was allowed to cool to around 90 F before adding 400ml of filtered saline solution to aqueous solution in 1qt jar

-SWIM realized that he forgot to add an additional 23g NaCl so he threw the 23g into the jar and shook vigorously until it had dissolved.

-Jar was placed in the refrigerator for 3 hours, no precipitation was seen. The pH was adjusted to 7.4 using janitorial ammonia.

-Lighter clouds of material began to be visible at around pH of 6.8. It looked just as he expected it to.

-Jar was placed back in the refrigerator overnight.

-In the morning the solution looked just as it had the night before. There was no layer of precipitation at all. It looks just like you would expect when the carbolides fall out but they seem to stay in suspension rather than precipitate to the bottom.

So the question is, where should he go with it now? He thinks he should just give it a big splash of ammonia and see what happens. And whiterasta, any status on a detailed tek? Thanks for the help fellas.