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Questions/advices regarding Tao of Rue Extraction Options
 
blazR
#1 Posted : 12/21/2012 10:50:26 AM
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Hi,

I've been lurking around for some time, but this is my first post.

I plan on doing the Tao of Rue Extraction in the nearest future, but have a couple of questions.

1. I plan on using fumaric acid instead of vinegar, but wouldn't that mean that the harmalas will prepicitate af fumarates in the end instead og HCl salt?

2. I can only find data suggesting that the HCl's are insoluble in saturated saltwater solutions, is it the same for most salts of harmala's?


Best regards & have a nice trippy christmas!
//blazR
 

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Infundibulum
#2 Posted : 12/21/2012 11:20:50 AM

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why do you plan on using a less common acid than vinegar for the process? Why fumaric and not acetic?

As for the solubility, only hydrochlorides are insoluble in NaCl-saturated solutions. It follows that (at least in theory) fumarate salts will be insoluble in sodium fumarate-saturated solution and so on.

You really have no reason to deviate from the tek, salt and vinegar are abundant!

Also, welcome to the Nexus!


Need to calculate between salts and freebases? Click here!
Need to calculate freebase or salt percentage at a given pH? Click here!

 
blazR
#3 Posted : 12/21/2012 11:54:59 AM
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The reason for fumaric acid insted of acetic acid is because I have an ammount of fumaric acid, to avoid the smell of acetic acid and because of this comment:
Quote:
Day Trippers fumaric acid approach leads to chunkier crystals later


I am no chemist, but I know a little.. What confuses me is that it seems like adding NaCL to the solution will form harmala HCl's?
I could see where the chlorine in HCl come from(NaCL), but does the hydrogen just come from atmospheric air?

Isn't it a "rule" that acetic acid forms acetate, fumaric acid forms fumarate and so on?
I don't understand if the harmalas prepicitate as HCl unregarding which acid you use.

Thanks for the welcome BTW Smile
 
Infundibulum
#4 Posted : 12/21/2012 12:19:16 PM

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Well, who cares about chunkier crystals while you're doing your extraction...
if you want them chunkier, then

1. purify them fairly well
2. convert to freebase
3. salt them with fumaric acid
4. see for yourself if you get "chunkier" crystals

I see your point with vinegar smell thought; in which case use less vinegar.

Quote:

I am no chemist, but I know a little.. What confuses me is that it seems like adding NaCL to the solution will form harmala HCl's?
I could see where the chlorine in HCl come from(NaCL), but does the hydrogen just come from atmospheric air?

Isn't it a "rule" that acetic acid forms acetate, fumaric acid forms fumarate and so on?
I don't understand if the harmalas prepicitate as HCl unregarding which acid you use.

the hydrogen is already in place, all alkaloids in acidic solution have this extra hydrogen (or are "protonated" in technical terms)

As for the precipitation, it has to do with dissociation equilibria. First of all, there is no such a thing as (say, for the sake of argument) harmine acetate in solution. Solid harmine acetate upon dissolution in water dissociates into the positively charged protonated harmine and the negatively charged acetate, both just float around in equal proportions, bumping onto each other occasionally and what not.

Adding NaCl in a harmine acetate solution means that the NaCl will also dissolve into the positively charged sodium and the negatively charged chloride. All molecules will be bumping onto each other occasionally and the positively charged harmine will have the chance of bumping onto the negatively charged chloride. When the latter happens, transiently harmine hydrochloride will form and because it is poorly soluble in the cold NaCl-saturated solution it will be stabilised and drop out (precipitate).

Harmine hydrochloride will have occasionally the tendency to dissociate back to harmine and chloride, but the presence of a already big excess of chlorides from the NaCl saturation will stop it from doing so. Generally (but not exactly accurately) the more you have of something in a solution (chlorides in our case) the more difficult is to add more of it in said solution (chlorides from the trying-to-dissolve back harmine hydrochloride.

That's all in a nutshell.

Of course, in theory, you could use any other acid apart from vinegar in the process but in practice if you have not seen someone doing it then you may as well not try to add extra variables in a process that you do not fully understand. I do not remember reading about fumaric acid used successfully but I do remember seeing that if you use citric acid then the manske precipitation might take many days to happen.





Need to calculate between salts and freebases? Click here!
Need to calculate freebase or salt percentage at a given pH? Click here!

 
blazR
#5 Posted : 12/21/2012 12:31:12 PM
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Thank you very much for the explanation Smile It makes sense..

Okay, you're most probably right about using acetic acid in my "first" extraction and then maybe proceed to experiment with fumaric acid later.

But the guide does state:
Quote:
Boil the seeds with a dash of vinegar, citric or fumaric acid.



Anyway, thank you very much for the help for now Smile
 
blazR
#6 Posted : 1/14/2013 9:45:48 PM
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Okay, I started an extraction of 50g. P. Harmala. I froze them for a couple of days before grinding them to powder.

I placed the powder inside 2 layers of cloth and cooked it 3 times and 1 more time with the seedmush not in cloth, filtered a lot and added a NaOH solution Smile

Freebase harmala alkaloids settling till tomorrow Very happy
 
blazR
#7 Posted : 1/16/2013 7:08:41 PM
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I now have ½g harmala HCl alkaloids. At the moment I'm trying to get more to precipitate.

Will most of the harmala's fall out at PH 4 or should I acidify further?


Regards
//blazR
 
Ilex
#8 Posted : 1/16/2013 7:54:19 PM

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I'm not sure on the pH optimum for precipitation, but a half gram of alkaloids from 50 grams of seeds is only a 1% yield, and you would expect to get closer to a 5% yield for average rue seeds. Are you sure your solution of NaCl is fully saturated based on the volume of liquid? I would guess the salt concentration is more important than the exact pH, I'm not a chemist though. You could also try heating the liquid until it reduces in volume, that would concentrate everything in it. Then stick your solution in the fridge overnight to promote precipitation.

When I did this tek, I just added excess salt (it didn't all dissolve), and collected the mix of alkaloids/excess salt from the bottom. Then converting them to freebase form strips away the residual salt, leaving just the alkaloids.

If you want "chunkier" crystals, remember that the size is related to the speed at which they form. Once you have the alkaloids in freebase form, you can try recrystallizing by dissolving them in a minimal amount of non-polar solvent and then allow the solvent to evaporate slowly, this should form bigger crystals.
 
blazR
#9 Posted : 1/16/2013 8:06:27 PM
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I added 195g NaCL for approximately 2L of liquid, after filtration of the harmala alkaloids I added another 100g NaCL.

If nothing precipitates over night I might try adding even more NaCL. Or maybe basify the solution for precipitation of freebases(Somewhere in the Tao a note is added about basifying again for more product).

I know 1% yield seems pretty low, but I'm quite confident I can pull more product out - I hope so anyways. My last extraction was only on 10g of rue but totally unsuccessful, so 1% yield is about okay Razz I had hoped for 2% at least
 
blazR
#10 Posted : 1/17/2013 3:48:14 PM
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No more harmala HCl's had precipitated over night, so instead i basified the solution till it got milky because of harmala freebases precipitating.

Actually, if I end up with the same amount or more as the HCl, it would be nice.. I have used NaOH - can I just wash the freebase in cold water a coupple of times to remove any NaOH residue or is there a better way?
 
blazR
#11 Posted : 1/22/2013 6:38:32 PM
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What the hell?!

I freebased the solution with NaOH and let it sit for at least a couple of hours, then filtered the solids from the solution and let the solids dry.

When completely dry it was weighed; 5,2-3g. Confused Isn't the harmine/harmaline % 2-7?
5,2-3g of freebase + 0,5g HCl must be about 12-14%, could that be correct?

I suspect some leftover NaOH, but NaOH is reacting with CO2 from the air and making Na2CO3, right? It was left to dry for 4 days...
 
 
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