Ph will not go higher

[merkin]

Merkin, how are your yields with Toluene?

I think it might still need a little more drying as there is the faintest whiff of Toluene still present. But also that sharp nose-curdling aroma-de-benzoic! Not sure if that means there's still a bit of actual benzoic acid in there too or that's just because of it's benzoic components?

Anyway, a startling 4.311g from 100g powder (bridgesii skin to core but not including core). A CIELO pull of same powder gave around 3.884g but I stupidly lost a bit to the carpet.

There is also about 20-30mg worth left inside bottle and filter papers. But yeah, I'm pretty satisfied if this is mostly the fabled mescaline benzoate!

My solvent pulls were only two minutes. Two minutes stir, two minutes rest. You think longer might be preferable? The 5 days sounds interesting.

After realising I had 'failed' I took the sludge from the extraction, mixed some KOH water and shook it all with some more Toluene and retrieved some green-gold solvent from a nightmare emulsion. Maybe there will be some more after freezing that?

Thanks for the freezer note.

Yield was 0.95% of sulphate

Did you do this as per the A/B method (water with sulphuric into the xylene and evap) or direct addition of sulphuric into xylene?

 

[doubledog]

Did you do this as per the A/B method (water with sulphuric into the xylene and evap) or direct addition of sulphuric into xylene?

It was typical salting out with water and sulphuric acid, then evaping (and re-x)

 

[Twilight Person]

I also have 2 interesting updates:

1.) Formation of mesc fumarate from toluene is not desirable: fumaric acid is totally insoluble in toluene and so also the salt will precipitate so fast, that it only forms really voluminous clouds, which dont crystallize nicely. It is so fine that you cannot even decant it. Though it is mesc fumarate, because the mass is more than just the initial fumaric acid. Still maybe not the best route.

2.) mesc benzoate working too! I feel that concentration is just the issue. It seems way more soluble than it would make sense. A regular extraction might have 500 ml on 100 g cactus. So you would get like 2 g of mesc benzoate in 500 ml.

But I now got a really nice precipitation from 100 mg mesc benzoate in 2 ml.

That means you need to concentrate the toluene a lot and then throw your benzoic acid inside. Still you can maybe just go with 2 g instead of 5 g, because excess is not needed (can anyways form only 1 salt type).

From all the few mesc salts I got now (citrate / fumarate / benzoate) it looks by far the most beautiful. Benzoic acid forms really sharp long needles when re-x'ed. So I was initially thinking if it could be just mostly benzoic acid. But there is an easy check:

Win! But what is it? Benzoic acid? maybe.

Just take a small spoon sample of your material and throw it into water. mesc benzoate will dissolve if you crush it fine enough, while benzoic acid is practically insolube. Just use super tiny amounts. Like 2-3 mg salt + 5 droplets of water. Only the mesc benzoate will dissolve. If everything dissolved you got the salt.

So for benzoate I feel it just has to be quite concentrated, but still above benzoic acid crashing out. But I feel solubility of that is super high anyways.

Actually now when I check your toluene merkin you drop it from 600 ml. That is actually the opposite of highly concentrated. So I am not sure if my theory is right? But it would at least explain why all the others and me did not get any crystals upon initial addition of benzoic acid to a big amount of toluene ...




Still I have no possibility to check overall purity. So a true verification would be cool. I will send it to a friend who can analyze it!

Now the last thing I still hope I can do with my remaining few mg is to try if I can drop it from limonene as benzoate. Second important thing would be how low does it need to be concentrated. Is the concentration after extraction enough? That would be important, otherwise it's not feasible ... because you cant just evaporate limonene like you do with toluene. And back-and-forth extraction into a smaller amount of limonene would be laborious and probably wasteful, so this route would then be not interesting I guess.

 

[merkin]

The crystals obtained have been crushed and dried properly now, yield weight not much change at 4.282g but it would seem all toluene smell is gone - but the smell of benzoate is so acrid its hard to tell.

The next step before bioassy then would be cleaning or re-x. Since this process invariably diminishes the yield weight I would like to be sure of what I am doing so I would appreciate any suggestions or tek on how to proceed.

@twighlight - I think the temperature seemed to be far more critical in terms of precipitation than concentration in my case? I would say that because I did the CIELO method with the CITLO the mesc concentration would be similar vs solvent volume. It would certainly take a long while to reduce the Toluene to see if concentrating made a difference.

The thing is, as purity is not yet established the yield could possibly be contaminated at least with raw benzoic acid. I am not sure if the smell of mesc benzoate salt is close to the original benzoic acid smell? It certainly is still like that for my candidate.

Anyway, steps to clean or re-x? TIA

Just for interest's sake a comparison of the colour of the salted but room temp extraction (right) vs after freezer precipitation filtered (left). This would indicate that some reaction definitely occurred here!

 

[doubledog]

Formation of mesc fumarate from toluene is not desirable: fumaric acid is totally insoluble in toluene and so also the salt will precipitate so fast, that it only forms really voluminous clouds, which dont crystallize nicely. It is so fine that you cannot even decant it. Though it is mesc fumarate, because the mass is more than just the initial fumaric acid. Still maybe not the best route.

Fumaric is known to form fine sediment, which is difficult to filter/separate.
I tried direct precipitation method only once, with tartaric acid (dissolved in ethanol and added to non polar solvent) and it worked fine.

From all the few mesc salts I got now (citrate / fumarate / benzoate) it looks by far the most beautiful.

IMO mesc sulphate crystals are also very beautiful.

 

[doubledog]

The next step before bioassy then would be cleaning or re-x. Since this process invariably diminishes the yield weight I would like to be sure of what I am doing so I would appreciate any suggestions or tek on how to proceed.

I would try this, but don't know if it works, it needs to be tested:

Dissolve 1g of your benzoate product in 20ml of boiling water. Use 200ml beaker, to have free space for another water additions (most likely you will need to add more water in the process and we still don't know how much water is needed) ).
Keep adding water in small amounts (5 ml) till everything is fully dissolved, then let it cool slowly to room temperature, then put it in the fridge.

There are no diminished yields from re-x, no losses. Just keep mother liquor (or evaporate it) and use it in another extraction.

 

[merkin]

I would try this, but don't know if it works, it needs to be tested:

Dissolve 1g of your benzoate product in 20ml of boiling water. Use 200ml beaker, to have free space for another water additions (most likely you will need to add more water in the process and we still don't know how much water is needed) ).
Keep adding water in small amounts (5 ml) till everything is fully dissolved, then let it cool slowly to room temperature, then put it in the fridge.

There are no diminished yields from re-x, no losses. Just keep mother liquor (or evaporate it) and use it in another extraction.

Thanks dd, I will investigate.

As I am not yet sure of the purity of this yield vs benzoic contamination I rmembered something else I did when trying CITLO with MHRB - I made a concentrated solution of benzoic acid with Toluene at 40°C. The idea was similar to FASA as I was concerned by the apparent slow dissolving of the acid and thinking it would mix with the benzoate precipitation.

When that cooled it made these super clear and long needle-point shards. Very different in size, look and shape to the precipitation of the supposed Mesc Benzoate from the freezing Toluene.

Here's another pic for interest's sake

 

[doubledog]

I have the same experience, benzoic acid and mesc benzoate crystals are visually different. My m. benzoate was very similar to yours in appearance.
I don't think that benzoic acid precipitates together with m. benzoate in substantial amounts.

 

[merkin]

I have the same experience, benzoic acid and mesc benzoate crystals are visually different. My m. benzoate was very similar to yours in appearance.
I don't think that benzoic acid precipitates together with m. benzoate in substantial amounts.

Thanks - that's great, the marquis reaction was also overwhelmingly positive. It was the presence of the acrid smell that had me thinking.

So - I did what you said with the water re-x. Took about 80mls for the gram.

< *EDIT* - don't do this!! >

The water is not back to room temp yet but already there is a forest of beautiful, spiky, feathery crystals growing. It really looks awesome!

Can this be same procedure with the water be done with the other mesc salts too? I have citrate and fumarate made via CIELO. Fumaric acid actually worked very well with standard CIELO but I got mostly powder with a few long shardy crystals.

 

[doubledog]

That is perfect, I am glad that proposed procedure worked
Your approach preliminary confirms that mesc benzoate indeed have similar properties to benzoic acid.

Check this:

Citrate is very soluble in water, re-x procedure have to be different. I would try something similar as one would do in case of m. sulphate, but with less water:
dissolve citrate in hot water (start with 1ml, add very small increments till its dissolved, add acetone, mix and let cool slowly.

I've never worked with fumarates.

 

[merkin]

Based on the good results I put the rest of the m-Benzoate yield from the Toluene into water for re-x. 3.2g dissolved in ~ 220ml distilled water @ ~80°C. It was filtered and then left to cool, currently now cooling in the fridge.

The first gram I did has been filtered and dried - yield 824g. Used the same water for the second re-x so expect to lose roughly a similar amount. I am not sure whether evaporating the water is advisable or should it be discarded?

Anyway, a couple more pics - the new 3g re-x cooling, and the dried 800mg. Once the crystals were bottled I could inhale deeply and there is pretty much zero smell now, no solvent, no benzoic acid.

I checked that video dd and the Benzoic acid re-x he did produced the same long needles? Could it be this is just Benzoic acid?

 

[merkin]

Re-x completed and everything dried. Yield mass went from 4.282g to 3.806g.

Now as pretty as they are the resulting crystals have no smell, or even taste. And unlike before the re-x the marquis reagent was pretty much a 'no change' result. Very different to the citrate from CIELO and the earlier test on the crystals from the Toluene before the re-x.

That doesn't make sense to me at all.

 

[doubledog]

That really is strange result. Could it be that you have there some excess benzoic acid? What amount of acid you used?
Don't throw away the water, you still don't know for sure where is your desired mescaline.

 

[Twilight Person]

unlike before the re-x the marquis reagent was pretty much a 'no change' result

So this means that marquis test was negative result = No amines? I have to say this all sounds pretty much like you were handling pure benzoic acid to me :surprised :surprised

It sounds weird that you needed 80 ml to dissolve like 1 g. It should be super soluble in water. In comparison benzoic acid dissolves like 1 g in 30 ml water. That is a pretty low solubility and that is what you also seem to have.

I also made a very little amount of mesc benzoate just to verify its properties and it was definetly super soluble, just as it should be regarding being a salt ... And I created it from the very basic pure compounds so I'm quite sure my results are really meainingful. Here is what I did:

137 mg mescaline freebase -> 2 ml toluene
80 mg benzoic acid -> 1 ml toluene

combined, initially no clouding. Let it sit for 24 h. Afterwards pretty crystals collected. Also put into freezer, then dried from toluene.

Resulting crystals: 176 mg from theory 217 (137+80) mg = 80 % precipitated. This must be mesc benzoate. Remainiong freebase mesc would stay in solution and remaining benzoic acid would stay in solution. Reason is solubility of benzoic acid is much more ethan 80 mg / 1 ml (I checked on that) and so what I got is the salt 100 %.

Now these crystals were extremely water soluble. Just 1 mg in 2-3 droplets water dissolves already. In contrast it will not dissolve in Aceton.

Could you just make a test by putting your long needles from water re-x into a super small amount of aceton? True mesc benzaote will not dissolve, otherwise pure benzoic acid dissolves super fast.

Because of this I have the feeling that this water re-x sounds more like it would be benzoic acid?

 

[merkin]

Could you just make a test by putting your long needles from water re-x into a super small amount of aceton? True mesc benzaote will not dissolve, otherwise pure benzoic acid dissolves super fast.
Because of this I have the feeling that this water re-x sounds more like it would be benzoic acid?

I think you are correct. It dissolved very easily in acetone.

I guess I screwed this all up! So the re-x'ing just threw away all the mescaline then? The marquis reaction before this was very positive.

What would have happened to any mescaline then? Could it still be in the water?

 

[doubledog]

It sounds weird that you needed 80 ml to dissolve like 1 g. It should be super soluble in water. In comparison benzoic acid dissolves like 1 g in 30 ml water. That is a pretty low solubility and that is what you also seem to have.

This is very different from my experience, my benzoate product was not very soluble in water, definitely not super soluble. I was not able to fully dissolve it in ratio 1g per 20 ml of water. And it was active, it produced typical mescaline effects in low dose, so I assume it has low contamination with benzoic acid.

 

[Twilight Person]

So I cant prove if my precipitate really is the mesc benzoate, but just because of this solubility tests it sounds quite like the way I assume it. I will try to get an analysis on that and then this may clarify.

I guess I screwed this all up! So the re-x'ing just threw away all the mescaline then? The marquis reaction before this was very positive.

So as I can not prove so far that I created the correct salt, I cannot be safe on what happened here, but it sounds to me like you had a mix of mesc benzoate and benzoic acid. Then upon using water you dissolved the mesc benzoate easily and the benzoic acid upon higher temperatures and adding more water. Then the benzoic acid precipitated again when cooling and formed those long needles. So you did not loose anything, but just made a separation of both as benzoic acid should have a really low water solubility (3,4 g per 1 l water according to wiki). Now would have the tedious job to evaporate the water, but then whatever remains should be marquis positive. I wrote that benzoic acid dissolves like 1 g per 20 ml water in the last post, but then that was wrong and the other value from wikipedia is right.

 

[doubledog]

I also cannot prove anything, just assume from my experiments (and experiments of others) and one bioassay. Whole benzoate topic is still not explored properly and there are lot of unanswered questions.
We need more experiments and tests.
Re-x in water would most likely not work well if lot of benzoic acid contamination is present.

 

[merkin]

I will evaporate the water but cannot believe there can be much of anything in there!

So all in all, was the entire CITLO extraction a failure or were those crystals in this post photo, obtained from ice cold Toluene much more than benzoic acid? The marquis reaction was strong, but that just indicates presence not quantity. It did have a very strong and acrid benzoic acid smell.

Basically nothing more than drying those crystals and then dissolving in water and so on so it all points to the fact that CITLO on cactus powder with lime is not very successful or do I have this wrong?

One lesson learned is don't try and re-x the CITLO results with water.

 

[Twilight Person]

I now have some more insights into the benzoate. Really trying to figure out how this can be easily created, because it might be free of hit-and-miss tactics with removing enough or too less/much water. Now I tried it with Limonene. Will post in big thread because it will fit there more, it works really great, but then the initial extraction (which is for the most part just like 69ron limonene TEK) does not work, because it will just emulsify unlike ethyl acetate which nicely can be decanted