"FASW" Titration of DMT from toluene- is possible?

[pete666]

Hi guys,

what do you think... Is "FASW" titration possible with DMT from toluene pulls? Not ordinary FASW salting, just something similar to HCl titration of mescaline. Let's say adding some RO water with precise addition of FASW and proper mixing. The reason is to have immediate information about DMT content in current pull without subsequent evaporation and wash. And to save fumaric acid.

Thanks for any opinion!

 

[pete666]

Well, I seem to have to try it

Alternative could be HCl titration and subsequent A/B with FASW. Any ideas?

 

[blue.magic]

I thought about that too since you can also easily detect point of neutralization using indicator such as nitrazine yellow (this works really great for mescaline).

Are you sure fumaric acid is insoluble in toluene? (it is insoluble in benzene at least)

One disadvantage would be water evaporation, potentially oxidizing some of your product and less purity as you may be left with alkaloid gunk trapping other impurities.

There is only one way to know for sure

 

[pete666]

I will check the use of nitrazine for my next mescaline or dmt extractions, thanks for tip

I don't know about how soluble the fumaric acid is in the toluene, but it shouldn't be difficult to test it. Anyway, FASA is used in "FASA Method Precipition From Xylene - No More Need to Evaporate!" section of post The FASA Method: A Summary - DMT Fumarate and Beyond for toluene, so it should work.

Water evaporation should not be problem at all, I would say. Once it is fumaric salt, it is safe.
Impurities can be removed by washes/re-x

I would like to know whether PH has the same impact on the purity here like it has in mescaline extractions...

Any other thoughts are welcome, so then I can decide whether it makes sense to try this way or not.

 

[blue.magic]

I will check the use of nitrazine for my next mescaline or dmt extractions, thanks for tip

You can check out an1cca's notes on mescaline analysis. I also reproduced his extraction method making pictorial about it and it works great.

Nitrazine yellow is a bit pricey but it will last you a lifetime since it is used in tiny amounts in high dillutions.

Water evaporation should not be problem at all, I would say. Once it is fumaric salt, it is safe.

I would like to know whether PH has the same impact on the purity here like it has in mescaline extractions...

Yeah sorry I didn't realized it is in salt form. Fumarate can be even baked, it's very stable.

I was never able to "burn" DMT even with phosphoric acid, it seems more resilient than M.

 

[pete666]

I had both mescaline hcl and dmt fumarate in an oven for quite long periods and didn't have any problems with any of them. But I never go higher than 70C

 

[pete666]

Just to let you know... I am not convinced I feel I could do the fumaric acid titration directly, so I decided to do HCl titration first and once I know the amount of dmt in the solution, I can basify it back and do FASW to get dmt fumarate.

I did the titration yesterday and it worked without problem. It seemed to be slower than for mescaline, but it just can be false feeling. With mescaline the PH was very high at the beginning and then gradually moved to 6-7 as I have added the HCl. With dmt it was slightly above neutral from the beginning (I was afraid there is not much in there, but it was) till the end. The titration was done with temperatures about 60C

I am still planning to do some tests later, so the fumaric acid titration might be tried later, if I get feeling it is possible

 

[downwardsfromzero]

You only need to titrate a small, known volume of your DMT solution with HCl. Then you can do a bit of maths and add the correct quantity of fumaric acid to the remaining (also measured) volume of solution. You would need to know the concentration of your HCl accurately for this to work.

Do you have a burette, because, of course, this is the classic apparatus for titration.

 

[pete666]

In fact I don't mind titrating everything with HCL and subsequent basification and FASW. This step will probably add to the purity. But it is just a guess.

I know the HCl concentration, it is labgrade diluted by me. And I am using just pipette. It may not be as precise, but this method for previous extractions of mesc was about +- 5-10% estimate/real, which is enough for me. And it is caused mostly by my impatience - biger amounts of acid for steps so I get too low with the PH at the end.

 

[downwardsfromzero]

OK, but wouldn't you rather save your reagents, and minimise the volume of the extraction? Otherwise you're using twice the amount of base and essentially wasting the HCl. [Edit: OK, unless you're processing unseemly quantities of DMT this is actually trivial!]

I suppose if you pull from the rebasified DMT.HCl into fresh NPS that's an extra A/B cleanup so purity might be marginally improved.

Following the titration with a pH meter alone will give different results for fumaric acid than with the HCl. Fumaric acid is dibasic, and somewhat weaker than HCl.

What you've outlined will, of course work! I'm just throwing some thoughts around

 

[pete666]

Thanks, I am thankful for any thought!

OK, but wouldn't you rather save your reagents, and minimise the volume of the extraction? Otherwise you're using twice the amount of base and essentially wasting the HCl. [Edit: OK, unless you're processing unseemly quantities of DMT this is actually trivial!]

Yes, no problem with such quantities. No plans for mass production

Following the titration with a pH meter alone will give different results for fumaric acid than with the HCl. Fumaric acid is dibasic, and somewhat weaker than HCl.

Please could you elaborate more? Do you mean just slower reaction or should I expect anything else?

 

[pete666]

I decided to do HCl titration first and once I know the amount of dmt in the solution, I can basify it back and do FASW to get dmt fumarate.

Just for the record : 60 Celsius FASW was added in steps into based dmt solution heated to 60 Celsius within 10 minutes with rapid stirring. PH was measured just to assure it won't go acidic, so there will be no excessive fumaric acid. The amount added was equal to estimated amount of dmt in solution given by previous HCl titration.

So it seems direct fumaric acid titration of toluene can be done, so toluene can be immediately used for another pull. And of course, there is immediate information about amount of dmt in the current pull, so information is available whether another pull is necessary.

 

[pete666]

Sorry to say that, but final evaporated amount is not as expected. Something went wrong and I don't know what. Likely fumaric acid in result? Or lost spice in np while doing FASW? Maybe errorneous HCl titration. Many things could go wrong
So I do not suggest this procedure yet. It is not confirmed!

 

[pete666]

We can exclude fumaric acid contamination. The evaporated stuff was fully dissolvable in small amount of water. So some fumaric acid (very) likely ended in the toluene.

18% in final content is missing compared to HCl titration estimate. This is quite a lot, but I might have done some mistake.

Never mind, this method is quite promissing, especially when followed by ACTIVATED CARBON wash on the red spice. Seems to be MUCH more rewarding compared to IPA wash or re-x.
I will give it a try again. And I might be surprised if missing dmt will have been recovered from reused toluene.

If you had any suggestions, please give me a shout!

 

[downwardsfromzero]

How did you account for the 18% missing product?

Recovery as freebase?

(Activated carbon will also hold on to some of the goods)

 

[pete666]

I had estimated dmt amount given by HCl titration. Then basified and salted by FASW. I was targetting the estimated dmt amount by fumaric acid amount. That was done like titration, I was adding small amounts of FASW and was checking pH. It turned acidic exactly at the point where I expected, so I thought the amount estimate is confirmed and the fumaric acid titration is going well.
The problem was there was 18% missing after evaporation. And in fact there had to be missing even more, as it was done with toluene, so the extract has wider spectrum. I don't have idea how much of the result could be some kind of fumaric form of anything and how much is something else. But weight to weight it was missing 18%.

I am planning to do just the HCl titration, then basify and weight the result, to confirm this part is OK. I might have bad calculations for titration? My calculator says I need 4,36ml of 3,7% HCl and 0,308g of fumaric acid for each 1g of dmt.

Could anyone able to do so to confirm it is right?

 

[pete666]

Well, I proceeded with other extraction, but this time I did HCl salting/titration from the (few times reused)toluene. It estimated 2,7% contents of the alkaloids. I have pulled(after basification by NaOH) it few times with hot(60C) heptane and recrystallized in a freezer. This yielded 1,33% of white crystals and 1,56% of yellow fraction, which after drying crystallized to hard yellow crystalline powder. The yellow fraction was not recrystallized for better purity, because the fuller spectrum might be preferred by some.
Both fractions were FASA'd to get dmt fumarate in next step.

This approach seems to be better than direct FASW salting where some problems were detected before. The result (2,89%) is in line with the estimated 2,7%, which is much better than when fumaric acid was used for salting/titration. Re-x with heptane is far easier than re-x of fumarate with IPA, which hardly worked for me.

For the white fraction - even last traces of yellow were removed when doing FASA. I used hot acetone for FASA, put it there within a minute (not slow addition), stirred it and let it sit for about 20 minutes to hour. Then I poured off the tone and pure white fumarate was acquired. If I let the tone with the fumarate for a day, the traces of yellow covered the top of the white fumarate. I suspect it stays dissolved in the tone when hot and precipitates when getting to room temperature.

For the yellow fraction - yellow fumarate is the final result. Which was expected and appreciated

Anyway, the results are :
1. Toluene seems to be good for initial extraction. It gets everything out of the basic MHRB solution.
2. HCl salting/titration is good for getting goods out of the toluene. The toluene can be immediatelly used for next pull and we know whether next pull is necessary. And there is no need to reduce the np for freeze-precip, we can reuse it all
3. Hot heptane pulls leave behind a lot of impurities in the water(mostly the red color, hot heptane is yellow) and they serve as a re-x at the same time, which separates the yellow
4. Classic FASA for fb=>fumarate conversion is much better than salting/titration by FASW. It generates better crystalls than water crystallization. Much easier to work with

 

[Loveall]

To salt DMT from Toluene, benzoic acid powder is a great option (CITLO). Simply dissolve benzoic in slight excess directly into the toluene. If desired a pH strip can verify salting is complete and be a rough titration indicator, along with cloud formation. There is a huge process window (benzoic acid won't saturate in toluene until above 87mg/g, where units are mass of benzoic acid over mass of toluene). Beautiful DMT benzoate xtals crash, usually very clean as other impurities seem to stay in solution (no need to worry about pesky biological stuff that partitions into both water and toluene).

 

[downwardsfromzero]

So, is DMT benzoate stable in the presence of a little moisture then? Have you kept the crystals long enough to make any observations on this kind of stability yet? It does seem like the rather non-polar benzene ring of the benzoate anion will help in this respect.

And, incidentally, I'll comment here because I forgot which thread the question about xylene solubility was, but looking at the solubility data I think it it safe to say that benzoic acid will be soluble in xylene to a similar extent to that of its solubility in toluene but likely slightly less. I would expect lower solubility (in mg/g) in part because of the higher molecular mass of xylene, and because the extra methyl group possibly adds an extra 'alkanic' quality to the solvent making it a bit more like heptane. Looking at the solubility in benzene - it's about 10% higher - it seems reasonable to expect that this is likely to be the case, although we can see that at lower temperatures the molar solubility is actually lower for benzene hence my hesitancy to be to exact about this. Paper attached.

The take-home information from all this is that if you wanted to dissolve a lot of benzoic acid in an aromatic solvent you'd need to warm it up (not that this is strictly directly relevant to our purpose here).

 

[Loveall]

benzoic acid will be soluble in xylene to a similar extent to that of its solubility in xylene but likely slightly less

I think you mean benzoic acid solubility in xylene would be lower that the in toluene