Does concentration affect harmine and harmaline precipitation

[Daaren]

I am extracting alks from rue following harmala extraction and separation guide.

I did this procedure many times in the pat but it is the first time i separate harmine and harmaline.

At the separation step i used a saturated sodium bicarbonate solution to precipitate harmine
Which gave me lots of alks.

At the harmaline precipitation step i used sodium carbonate saturated solution and almost got no precipitation.

I had to use almost 200ml water saturated with sodium bicarbonate to precipitate the harmine.

Being left with about 750ml of liquid after adding the saturated sodium carbonate water
I was wondering if the volume might be the reason for such a low yield.

Should i and can i reduce this water to then basify more??

My ph reading this morning ( after letting the harmaline settle overnight) was of 9.75

Maybe ph not high enough?


So to resume the question: does the concentration of the solution affect the precipitation? Could i by example (an extreme example here) dissolve 30mg of harmine in acidic water and precipitate almost 30mg out of a 500ml volume?

Thx! In advance for your input guys

 

[downwardsfromzero]

You're right, harmala alkaloids will precipitate better from a more concentrated solution.

One way of avoiding dilution is to place the beaker of concentrated harmala solution inside a larger container into which some concentrated ammonia solution is also poured, and the larger container is sealed with a lid. That way the ammonia diffuses and dissolves into the harmala solution in the beaker without becoming significantly diluted. This can also be done after first separating the harmine with sodium bicarbonate.

One of the things with using carbonates is that the carbon dioxide that gets released also takes time to diffuse out of the solution so the pH changes can be a bit weird and unexpected.

Should i and can i reduce this water to then basify more??

During the process of evaporation carbon dioxide will escape and this may potentially be enough to precipitate the harmaline. At room temperature, sodium carbonate reacts with carbon dioxide to produce sodium bicarbonate and I think it is this process that has been messing up your pH changes. Fortunately, sodium bicarbonate starts to decompose at about 98°C so simmering your solution may well help.

So to resume the question: does the concentration of the solution affect the precipitation? Could i by example (an extreme example here) dissolve 30mg of harmine in acidic water and precipitate almost 30mg out of a 500ml volume?

The other thing to mention is that freebase harmala alks appear to show some level of solubility in neutral water. So, by keeping the volume of water to a minimum the amount of precipitated alks can be maximised. In your example it's likely that a significant proportion of the harmine would remain in the solution, possibly as unfilterably small microcrystals.

 

[Daaren]

Thank you so much for the well detailed answer Downwardsfromzero.

So yesterday after work i set my beaker on my stirring plate with the ~750ml of liquid to evap at 91c , stirring with fan on.

It is so humid these days 88+ % humidity that after 2.5h only about 150-200ml had evaporated

I turned of the plate before bed and let it rest all night.

No change , nothin precipitated.

This morning i added about 200ml of saturated sodium carbonate water ( i have to find ammonia its hard to find around here)
And i was only able to bring the ph of the solution to 10 before i was back to my initial volume of ~750ml

I was a bit in a rush this morning before work and i have to admit i wanted to see results...

So nothin happened overnight in the slightly reduced solution ( ~500ml)

BUT: i weighted the harmine that is now dry and the harmaline i recovered yesterday
The results were: 11.95g harmine and 750mg harmaline.

The harmine part seems heavy for a 300g extraction no?

Could my harmaline have precipitated when i added the sodium bicarbonate water?

By the way : i did 3x the basify, acidify, salt cleanups.

 

[downwardsfromzero]

Great to hear you've been experimenting. Even a null result is useful information.

11.95g harmine from 300g seeds is just shy of 4% which isn't completely unheard of. Some seeds contain 7% total alkaloids, and if more than 50% of that is harmine (which is entirely possible) then your figure seems reasonable. It could be inflated if there is a significant amount of harmol present.

There's probably a good amount of harmaline still present in solution. How does the solution look under UV? Finding a way of bumping up the pH seems to be a priority. You could try roasting your sodium carbonate in the oven for a while. Washing soda slowly absorbs carbon dioxide from the air so if yours is somehow a bit old a significant proportion may have turned into sodium bicarbonate and scuppered your ability to raise the pH any higher.

My limited amount of observations with sodium bicarbonate suggest that little if any harmaline drops out along with the harmine.

 

[doubledog]

My experience is that sodium bicarbonate precipitates quite a lot of alks, too much to be just harmine.
This is also in line with observations from VDS protocol thread, that separation of harmine and harmaline occurs at much lower pH.

 

[Jagube]

I don't reduce my brews; I base them straight away. Haven't noticed a loss considerable enough not to warrant such a time and energy saving measure.

Ammonia is recommended for separating the two alks.

 

[downwardsfromzero]

My experience is that sodium bicarbonate precipitates quite a lot of alks, too much to be just harmine.
This is also in line with observations from VDS protocol thread, that separation of harmine and harmaline occurs at much lower pH.

Yes you're right, I overstepped there. Maybe it's time for some more experiments. Adding the bicarb very cautiously should minimise the harmaline co-precipitation, surely?

I'll take a look at the figures and consider what might be a more effective base for this separation. There must be a more effective way - or is it unavoidably a matter of repeated A/B cycles?

Whatever, the VDS protocol thread is worth a read through for getting a grasp of some of the intricacies and foibles of harmala precipitation.

Particularly here:

Another observation I have made in the past was that sodium bicarbonate could not precipitate DHH out of solution. However, in a combined harmine/DHH solution it succeeded in precipitating a lot of it. And when harmala freebases are filtered out of solution, it takes some base (pH-differential) to restart the precipitation from the mother-liquor... I think the author observed the same thing when looking at the spikes in his titration-diagram. Nature works in mysterious was...

 

[doubledog]

Adding the bicarb very cautiously should minimise the harmaline co-precipitation, surely?

Probably yes, with pH kept low, hopefully just harmine precipitates.

I'll take a look at the figures and consider what might be a more effective base for this separation. There must be a more effective way - or is it unavoidably a matter of repeated A/B cycles?

Would be great to find some specific base just for this separation. What about some very weakly basic salt?

 

[Daaren]

Yesterday evening i set the heating plate on a timer and let it run for part of the night.

This morning i found that i was left with about 350-400 ml of liquid. A thick crust of covering the whole surface. No precipitation and the liquid still brown.

I left it like that.

Just came back from work (14h later) now the liquid is clear and everything settled at the bottom.

I now understand a reason why it is not recommended to use carbonates.

How could i recover the alks mixed with the precipitated ?sodium?

The solution did react to black light.

And i found some ammonia today. Will try to separate the harmine i first extracted again this weekend when i have a bit if time ( working 75h/week these days)

 

[ava69]

Hi Daaren, I've seen you around...

In part 10, post #12, explain how to separate harmine from harmaline easily, I dissolve the purified rue hcl extract into water on a stir mantel, and as the stir mantel spins....add drops of 10% ammonia to precipitate only the harmine 1st, then a very small middle fraction (harmine + harmaline), then a final fraction which is only harmaline.

Journal: 50 Sublingual | <span style="frontcolor:pink !Important ;">High Pobability of Braindamage by Creepy non tested Drugs (forced by scammer 69ron)</span> | DMT Ayahuasca journeys over a years time - Pharmahuasca - Welcome to the DMT-Nexus

Long time chemist, so any questions just shoot. I prefer using 10% ammonia from hardware store (janitorial). Super good PH meter: Apera Instruments ph20 ph meter.

 

[Daaren]

Hi Ava69
Since i didnt have ammonia on hand i used sodium bicarbonate first and then sodium carbonate.

I have a bunch of seeds but id be interested into trying to salvage this harmaline precipitation and learn from the experience.

How would you suggest me to separate the harmaline that precipitated with the sodium into my mother liquor?

Since i reduced i have a 1/2 thick of salt like deposit at the bottom of my beaker.
And this precipitate glows when exposed to uvlight so my guess would be that the harmaline precipitated with it.
The liquid is now much clearer.

I used to use full spectrum alks but after I read your thread on hpbcd subligual dmt I wanted to give it a try.

I now have everything required on hand just need to finish this extraction and convert a proper amount of harmaline to thh.

I am really looking forward to experience the blissful dreams aya brings in a more "lets say" accessible way.

Thank you for your help

 

[BongQuixote]

I use ammonia for this too, a lot less messy and more exact. When using the PH meter to find the separation point between harmine and harmaline, do not rely on any exact PH reading as the cutoff point between harmine and harmaline. It varies with batch and concentration. Best method I've found is to add ammonia dropwise until you get harmine to start precipitating (clouding). When that happens, PH will drop. Take a note of what the PH reading is after the drop. Keep adding ammonia, a drop at the time, and you will again see a rise in PH, more precipitation and then a PH drop back to the value you made a note of earlier. Once PH stops dropping back to that point when you add a drop of ammonia, STOP! You have now precipitated the harmine. Filter it out and keep adding ammonia until harmaline starts to precipitate, still going slow.

One thing that can trip you up is adding ammonia too quickly, or not stirring while adding. If you don't you will create a spot where the drop lands with much higher PH, and harmaline in that area will precipitate as well. So go slow, keep it stirring and keep an eye on the PH meter. A drop or two too many could increase PH beyond what's needed for harmaline precipitation, especially when working with small amounts of liquid.

 

[Jees]

Yes an absolute pH separation point does not exist, variables play with it.

Most ideal is having circumstances that allow pH depressions to occur, the pH dips tell where you are, as explained in the VDS papers. In attachment pic ex VDS papers, the red pH dip reveals harmine dropping out, the green dip indicate the harmaline (DHH). The second one might as well be a little plateau instead of a real dip, but actually this is of complete non relevance since it is the first one where the separation occurs. After filtering harmine out (in the pic at aprox 45) it's just basing further to get everything dropping out what remains.

When I'm doing a very first basing of a boiled seeds rue soup to get all alks dropping out with no separating in mind in this stage, never a dip is to be seen in the gradual rise of pH. This soup condition are not good for having pH depressions there.

I second the use of ammonia for the finer pH plays like separation games.

Happy trials...

 

[Daaren]

Little idea to cleanup my mess:

Could i slowly and gradually add water ( 50-100ml/ 15min) heating and stirring to redissolve the excess of sodium
Hoping that the alkaloids wont dissolve into the mix and then filter?

 

[downwardsfromzero]

What makes you think that there is an excess of sodium [salt] in your precipitate - and which sodium salt for that matter? What if the precipitate is something else?

Which acid did you use in the initial cooks of the rue seeds?
Did you use distilled/deionised water, or something like tap water?
How much bicarbonate and carbonate do you think you've added so far?
What was the volume of the solution before evaporation?

Adding a little water and seeing if anything dissolves shouldn't do any harm.

 

[Daaren]

What would be the salt like substance precipitating from water that is saturated with sodium bicarbonate and that was reduced?

I only used vinegar in the extraction.
Not having distilled water on hand i used bottled water.

I used about 200ml of sodium bicarbonate saturated water and then at least 300ml of sodium carbonate saturated water.
The water was room temp.

Volume before evaporation was around 800ml

I did continue to add sodium carbonate water because i did not see any precipitation.

Heres a picture of the crust that was on the surface of the water

https://imgshare.io/images/2021/07/02/D5502DA7-B4D2-4B56-831E-00083F21CD4E.jpg


Current state of the harmaline precipitation.

https://imgshare.io/images/2021/07/02/20AE9855-1C36-4CD1-BB0E-21C75A0C3C5D.jpg


After filtrating out the harmine. The recovered liquid was bring yellow. It slowly and progressively turn to a more golden brown color
With time and evaporation.

Sorry guys for the links.

Trying to figure out how to share pictures. Will take a moment to read and find out tomorrow.

 

[downwardsfromzero]

What would be the salt like substance precipitating from water that is saturated with sodium bicarbonate and that was reduced?

I only used vinegar in the extraction.
Not having distilled water on hand i used bottled water.

Some of your precipitate will be calcium and magnesium carbonates, check the label on your water bottle - it should show the typical calcium and magnesium levels. Some of the precipitate will (or could) be sodium bicarbonate which has a limited solubility. If you could filter the solids as dry as possible using suction, that would be great. Then take a small sample of the solids and see what happens when you put a drop of vinegar on it.

I used about 200ml of sodium bicarbonate saturated water and then at least 300ml of sodium carbonate saturated water.
The water was room temp.

Volume before evaporation was around 800ml

I did continue to add sodium carbonate water because i did not see any precipitation.

Did you record exactly how much sodium bicarbonate and carbonate you used? Because this would be helpful in estimating how much sodium bicarbonate might have precipitated.

I think your best move would be to filter out the solids, wash them with distilled water then redissolve in vinegar, again using distilled water for dilution. Precipitate the alkaloids with ammonia, using a pH meter if you want to separate the harmine. The bottled water has introduced calcium and magnesium salts. These will keep precipitating when you add sodium carbonate, but not when you use ammonia (or less so, for the most part). To absolutely get rid of them you'd need to do a Manske precipitation with salt. That might be a sensible step now, before you try basing again.

Heres a picture of the crust that was on the surface of the water

https://imgshare.io/images/2021/07/02/D5502DA7-B4D2-4B56-831E-00083F21CD4E.jpg


Current state of the harmaline precipitation.

https://imgshare.io/images/2021/07/02/20AE9855-1C36-4CD1-BB0E-21C75A0C3C5D.jpg


After filtrating out the harmine. The recovered liquid was bring yellow. It slowly and progressively turn to a more golden brown color
With time and evaporation.

Sorry guys for the links.

Trying to figure out how to share pictures. Will take a moment to read and find out tomorrow.

It's a shame that site doesn't allow hotlinking so the pictures can be embedded. Another option would be to upload them here as attachments, using the 'attach' button at the top right of the post, or by checking the 'Attach files to this post' checkbox that appears underneath the post editor screen.

 

[Daaren]

Sorry for the lack of updates. I have been even busier with work lately.

I ended up throwing everything away.

The separation of harmine and harmaline went well. Observing the two ph drops following precipitation of harmine and the harmaline was fascinating.

I then proceded to convert the harmaline to thh using pure zinc. Following Ava69's
Thh conversion guide.

Once again everything went well, the solution was glowing of a beautiful cyan blue and then...

At the basification step i realised the ammonia i had might not be what i thought it was.

I had to add 800ml of ammonia to 200ml of vinegar/thh solution to get some precipitation,
At a ph of 7 a gel like white substance started precipitating. It clouded my solution and when i finally
Got my ph close to 9.5 then i got the usual "grainy" white precipitation that i was expecting.

Let it sit overnight and the next morning i was left with 3 phases. Clear yellowish water on top,
White gel in suspension and finally sand like deposit at the bottom.

Filtration of this solution gave me alkaloids covered with bits of a white soapy gel.

My guess would be surfactants.
What would you think?

https://ibb.co/pdVZPWx

I then shook my bottle of ammonia and it slightly foamed.
I guess ammonia should not foam or froth at all right?

Last week i found a reliable company to provide me with "pure" ammonia.
Got some 10% and some 28%

Will start over hopefully soon when i am done with this 7/7 rush at work.

Thanks to everybody who contributed to this post.

I learned a-lot through this failure and it was well worth it.

 

[Jagube]

Yeah, it shouldn't foam at all and there should be no gel.

For me, it gets sticky sometimes during the addition of ammonia and sometimes I have to stir manually, because the stir bar gets trapped in the sticky goo, but around pH 9 the stickiness dissolves.

Also, it's a lot of ammonia you put in there. When I basify, it's ~10 grams of THH in 300-400 ml water and ~100 ml 10% ammonia solution is enough to precipitate it.
I don't think surfactants act as pH buffers, but maybe a chemist can chime in?

Personally I like to put some HCl in addition to the vinegar to make sure the reduction completes. I've had vinegar alone not lead to complete reductions and having to add more, which led to undesirable dilution and having to use more ammonia.
The HCl tends to be eaten up quickly by the zinc and the remainder of it driven out, so after an initial acidification to a pH between 1 - 2 and a few hours, it's up to ~4 (depending on how much vinegar was used) and no HCl smell. I imagine the resulting solution has fewer ions floating around, which means I need less ammonia (less neutralization product -> less pH buffering)

 

[Jees]

Hi Daaren, never give up :thumb_up:

While your ammonia shouldn't foam, the gel is most likely zinc salts imho.
Zinc acetate is formed during the reduction stage between the vinegar and zinc dust. Zinc acetate then adding a carbonate base later forms zinc carbonate, adding lye later makes zinc hydroxide, we didn't ask for it but there you have your zinc salts. At low pH the zinc salts are liquid, at rising pH they start to flocculate, at further rising pH they dissolve again. In this post is a picture-set of various pH's and how those zinc salts behave. Your pH 9,5 might not have risen enough for the zinc salts gel to broken down again into solution.

Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols - Collaborative Research Project - Welcome to the DMT-Nexus

An1cca had bit of the same result:

Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols - Collaborative Research Project - Welcome to the DMT-Nexus

So harmine might co-precipitate with zinc salts, for that good reason I would leave the idea of reducing a mixed fraction of harmine+harmaline. Better to separate the two first (as you did) so one can precipitate harmine without zinc salts flocculants. Then reduce harmaline to THH, then base up to 11 or so at least to get rid of the flocculating zinc salts.

The exact pH points where the zinc salts re-dissolve under rising pH are also not fixed, depending on the base used and whatnot. In an isolated test (one test only !) lye seemed to need a lot of it before zinc salts redissolved, and under ammonia they dissolved faster (at least it seemed quicker). FWIW.