SWIM first dropped FASA into fresh limonene to see if the fumaric acid precipitated out, and it didn't. SWIM performed the experiment on a very small scale by dissolving about 50mg of freebase DMT into 30mL of limonene. When he added FASA to the solution, the solution immediately became cloudy, as expected. He left it overnight and what appeared to be the expected amount of DMT-fumarate had precipitated out as crystal slivers.

So what this experiment showed SWIM is that fumaric acid remains soluble in a solution of acetone and limonene (as with xylene or toulene) and DMT-fumarate is not soluble in limonene--otherwise SWIM probably wouldn't have ended up with any precipitate.

Unfortunately, SWIM's getting a little low on spice at the moment and doesn't have any botanical material to extract from, so he can't try this on a larger scale. But for his next extraction, he will use a botanical powder, mixed into a paste w/ water and lime, put into THP (w/o drying), he will run limonene through THP, and he will precipitate w/ FASA.

SWIM was considering using sodium carbonate, but he has recently decided to designate lime for extractions using limonene as the extraction solvent--because of its ability to hold water and break down plant material--and sodium carbonate for freebase conversion and bufo extractions--basically anything using acetone as the extraction solvent, as lime tends to float around a bit in acetone.

This is weird but not necessarily unexpected. SWIM's FOAF tried adding FASA into pure limonene limonene in the past and it actually precipitated out, contrary to SWIY's observations.

Why however would SWIY observation be "not unexpected"? Well, each person is using different materials. People buy different reagents from different vendors and even if everyone were buyng from the same vendor then there would be differences from each batch to another.

The MSDS of the limonene SWIM's FOAF uses states that it is food grade and contains 95-100% orange terpenes. This range is most likely stated after analysing the orange peel distillation product from plenty of different batches. Could it be that SWIM has 100% limonene and fumaric adid precipitates out? Or could it be that SWIM has 95% limonene and teh 5% rest cause precipitation of the fumaric acid? Same goes for the fumaric acid and acetone people are using.

SWIM believes that this can be a fair reason for discrepancies across experimentors sometimes. One always need to test his materials and do Control tests (control test in this case is no precipitation of fumaric acid after FASA addition in pure limonene)!!!

Since SWIM can do more extensive tests to find out if fumaric will precipitate and SWIY's tests seem to contradict SWIM's admittedly hasty test, SWIM will try it again. But the main test seemed to go exactly how it should, regardless, so SWIM has his doubts.

This is only amazing - pushing the frontiers of science

Seems SWIY was right. When SWIM added 10mL of FASA to 20mL of limonene, fumaric acid precipitated out. This didn't seem to happen when he added it dropwise in the previous experiment, and there was no white powder left over, just crystals. This experiment did not seem to cause it to precipitate completely though.

However, SWIM's product turned to most definitely be DMT fumarate. SWIM decanted the completely clear limonene/FASA out of the container, poured a small amount of d-H2O into the container to collect the fumarate crystals, pour the solution onto a dish and evaporated in the oven. After it had dried, it scraped up as a waxy crystal, though notably less so than most waxy crystals SWIM encounters. SWIM washed the product in acetone, the product grouped together, and SWIM fished it out and put it on the dish and back into the oven. The product dried to hard rocks of the same consistency as DMT fumarate.

SWIM hypothesizes that only a certain concentration of fumaric acid will remain dissolved in a solvent solution of acetone and limonene solution, depending on the solvent ratios. Perhaps titration with known volumes and concentrations could be used to determine this.

Fumaric acid doesn't seem to precipitate out of completely saturated FASA unless there's more limonene than acetone in the solution. SWIM doesn't have the equipment to do the exact tests he would like to, though.

What SWIM would imagine happened in his first test is that, as the amount of fumaric acid that does manage to stay dissolved in the binary solvent, reacts with and binds to the DMT, precipitated fumaric acid dissolves back into the solution, an the cycle continues until all the DMT has crashed out in fumarate form. If an excess of FASA is used, the precipitates will contain some fumaric acid alongside the product, but if added dropwise, a proper amount can be used and fumaric acid contamination will be insignificant.

SWIM's saving all of his FASA/limonene solution from the tests, what he's hoping to be able to do is possibly be able to use that to precipitate DMT fumarate out of limonene, rather than straight FASA. Hopefully there is actually a decent amount of fumaric acid able to dissolve into that, but maybe not.

Yes, that's most likely what happened.

Is the point of this to specifically make DMT fumarate or to get a DMT salt to precipitate from d-limonene?

If you want to precipitate DMT from d-limonene, I believe CASA (citric acid saturated acetone) would work much better. Citric acid is probably much more soluble in d-limonene than fumaric acid is.

Yes, the goal is to get the fumarate. SWIM may yet find an easy and feasible way to accomplish it. It may even work as is for extractions. It mostly depends on whether one could visually determine when the solution stops precipitating the fumarate and starts precipitating fumaric acid, which may actually be quite difficult.

Otherwise, perhaps the CASA could be used to crash out of the limonene, the limonene could be decanted, and the precipitate could be incubated in FASA to yield a fumarate product. This would depend on how easy it is to convert from the citrate form to the fumarate form. Has anyone tried converting a citrate goo to fumarate crystals?

Even if excess fumaric acid precipitates out, the acetone used to wash the precipitates could be reused as FASA. There has to be a certain concentration that the fumaric acid can be set to in the acetone so that it never precipitates out of it when added to limonene, though. SWIM has a suggestion for a test to figure this out: pick a small amount of dmt to simulate, weigh out the amount of fumaric acid expected to react with that amount, put it directly the volume of limonene expected to carry that amount of DMT, titrate with acetone while stirring until the fumaric acid completely dissolves, note the amount of acetone required and figure out the concentration of fumaric acid in that acetone. This may not work at all, but if it does work and has feasible results, it would be quite a leap.

Ugh, but that ^^ would require much more materials supplies and equipment than SWIM has available. Seems simple enough to just let the excess precipitate out, wash with acetone and recycle as FASA. SWIM couldn't imagine how there could be much if any loss, unless one added too little FASA (which may still yet be a problem if it can't be determined visually). The product should always be retrievable, and this is probably the biggest issue with experimental techniques.

If thats the case, that precipitated fumaric acid dissolves back into solution when DMT fumarate is formed, would it not be the same story when using naptha? i.e adding FASA to spice laden naptha would first precipitate both DMT Fumarate and Fumaric acid but as more fumarates precipate then the excess fumaric would be redissolved back into the acetone?

As swim has noticed when adding FASA to naptha/white spirit that a cloudy precipitate appears but after a while the precipitate seems to disappear. Does anyone know if DMT fumarate is soluble in naptha/white spirit?

SWIM's thinking about sticking with acetone for spice extraction. The only reason he would like to use limonene is because it's not miscible in water. Acetone's much cheaper and more readily available, though. SWIM just needs to refine his acetone drying techniques. If anyone has any viable solutions for using FASA with limonene, SWIM would still love to hear it. He simply doesn't have the resources to adequately explore this. It's simply too difficult to tell whether all the spice has precipitated or not.

He will try this with CASA followed by FASA when he gets some time, but he doesn't have high hopes. Hopefully this thread has at least made some headway or answered some questions regarding the topic, though, as there were many floating around out there.

Last time SWIM dropped CASA in limonene it didn't mix; it formed two layers, the bottom one being CASA and the upper one being limonene. It would be nice if SWIamor_fati or anyone else repreats and verifies this observation.

SWIM abandoned the CASA - limo route because he thought it was introducing uneccesary complications. But someone else might think of a use for this peculiarity.