Deinonychus
Bluelighter
- Joined
- Oct 20, 2012
- Messages
- 401
Hello all! I have a question about the stability of DMT when heated. I did indeed google and then UTFSE here on Bluelight and I haven't found an answer that is specific enough to answer my question, so I'm going to post it up here. I'm aware there is a DMT extraction megathread, and I read through a fair portion of it, but I ultimately decided to post this as a new thread instead of adding it into the extraction megathread because I want to ensure maximum visibility in the hopes that doing so will make it more likely that I will find an answer to the problem using the collective knowledge of this forum. So here goes...
To those disinclined to reading through the long-form explanation, I summarized everything at the bottom as four questions. Thanks!
Background:
I performed an extraction of DMT from Mimosa hostilis rootbark powder using NaOH and naphtha in a 'straight to base' extraction. The extraction was repeated with naphtha a total of four times per jar, to ensure that the yield was as high as possible, and for the last two of the four extractions, more NaOH was added and then followed by some NaCl to increase the polarity of the aqueous phase as much as possible. The organic layers of the four extractions were then combined, and filtered through filter paper using a Büchner funnel and vacuum pump, though the naphtha appeared to be completely devoid of MHRB powder particles upon initial visual examination, which was confirmed by a lack of any impurities on the filter paper when filtration was complete.
The final action was to put the solution of DMT in naphtha into the freezer, cranking the fridge to its coldest setting while also directing the great majority of that cold air into the freezer compartment instead of the normal fridge partition. Freeze precipitation then ensued, resulting in gorgeous freebase DMT at yields that really surprised me, considering that I had expected only 2/3 as much final product.
The problem:
While freeze precipitation worked perfectly for the first few jars of naphtha, for some reason the last few jars of the stuff yielded nothing when put into the freezer, despite being just as golden-colored as the first few jars. I cannot figure out why this would be! I tried adding some of the dried DMT freebase as a 'seed', as one would do with some crystals, with no result. I also eliminated a fair measure of the naphtha in one of the jars via plain old evaporation, but though the color of the solution got deeper and more vibrant, still nothing would precipitate out.
So could anybody perhaps venture a guess as to what might be causing freeze precipitation to fail? I checked the temperature of the freezer, and it was just as low as it had been for the initial few jars where the freeze precip worked great. Freeze precipitation is based on a very well-understood and simple process, that being the large difference in the solubility of DMT in naphtha as the temperature drops from warm, roughly 30 °C to almost -20 °C in this case. As the solubility of the stuff in naphtha drops with the temperature, the solution becomes supersaturated, causing some of the product to (slowly) crash out of solution. The process is so basic and fundamental that I can't figure out what the reason would be that it wouldn't work! Can anybody help me out with solving this mystery?
The options I have thought of as workarounds:
1. Further evaporate the naphtha. This leads me to ask the question of how DMT reacts to heat. Would it break down if I were to use a lab-grade hotplate to heat up the solution to aid in the evaporation? Is there a temperature above which the product will break down? Naphtha such as I have used boils somewhere between 30 and 90 °C, so considering that large range I can't predict specifically how hot it will have to be to boil, so instead of asking whether DMT is safe at a given temp (whatever the boiling point of my naphtha turns out to be), I'll ask if there's a limit to how high the temp can be allowed to go before degradation takes place.
2. Crashing out as a salt. I'm familiar with the fact that the DMT hemifumarate (one fumaric acid ion will bond to two ions of DMT) salt is for all intents and purposes insoluble in acetone, especially if you first saturate the acetone with fumaric acid, while freebase DMT and fumaric acid themselves are soluble in acetone. Fumaric acid is not soluble in naphtha, so you can't just crash the DMT out as hemifumarate from naphtha directly, but acetone and naphtha are themselves miscible. This leads me to wonder if it would work to saturate your acetone with fumaric acid, then add to naphtha/DMT solution. If the DMT and fumaric acid were then able to meet, the resulting salt would be insoluble in either the naphtha or the acetone, allowing it to precipitate out. This would be intended as a workaround for the lack of solubility of fumaric acid in naphtha itself.
However, I have no idea if saturating the acetone with fumaric acid and then adding to the DMT in naphtha solution would result in the salt or whether it would just further dilute the solution, with the fumaric acid becoming a contaminant, as my chemistry knowledge doesn't go that deep. Anybody have a better understanding of the concepts that underlie this theory?
In summary:
1. Does anybody have a clue why freeze precip would work beautifully for the first half of a batch of DMT in naphtha and yet not work for the second half?
2. Is DMT freebase sensitive to heat? Or better put since everything is ultimately sensitive to heat if the temp is high enough, at what temperature does DMT begin to degrade? This is pertinent to evaporating the naphtha solvent using a hot plate with teflon stir-bar.
3. Acetone and naphtha are miscible. DMT freebase is soluble in both solvents. Fumaric acid is mildly soluble in acetone, but not naphtha, and DMT hemifumarate is insoluble in both naphtha and for practical purposes, acetone. Thus could you precipitate out DMT hemifumarate from naphtha by adding fumaric acid saturated acetone dropwise, thus getting around the lack of solubility for fumaric acid in naphtha alone?
4. Any other ideas for either determining why freeze precipitation stopped working/for getting the goods out of naphtha besides the aforementioned evaporation or theoretical idea to crash out the fumarate? I'm down with getting it out as base or as a salt, as the salt can be subsequently liberated to base, but would prefer not to have to extract to aqueous solution as water is harder to evap than naphtha anyway.
Any help would be ultimate awesomeness and very much appreciated!
Thanks
D
EDIT:
To clarify, the contents of all the precipitation jars was homogenous prior to successfully precipitating from some of them. In other words the amount of DMT solute per volume of solvent was basically identical in all jars. This is why it confused me that the first few jars did precip properly and the last few did not.
It's also worth mentioning that when the unsuccessful precip jars are chilled to their proper temperature, they become massively hazy, to the point of being opaque. This seems to indicate that perhaps the precipitation is actually happening, but that the size of the resulting solids is so small that they are staying suspended in the naphtha rather than settling to the bottom.
To those disinclined to reading through the long-form explanation, I summarized everything at the bottom as four questions. Thanks!
Background:
I performed an extraction of DMT from Mimosa hostilis rootbark powder using NaOH and naphtha in a 'straight to base' extraction. The extraction was repeated with naphtha a total of four times per jar, to ensure that the yield was as high as possible, and for the last two of the four extractions, more NaOH was added and then followed by some NaCl to increase the polarity of the aqueous phase as much as possible. The organic layers of the four extractions were then combined, and filtered through filter paper using a Büchner funnel and vacuum pump, though the naphtha appeared to be completely devoid of MHRB powder particles upon initial visual examination, which was confirmed by a lack of any impurities on the filter paper when filtration was complete.
The final action was to put the solution of DMT in naphtha into the freezer, cranking the fridge to its coldest setting while also directing the great majority of that cold air into the freezer compartment instead of the normal fridge partition. Freeze precipitation then ensued, resulting in gorgeous freebase DMT at yields that really surprised me, considering that I had expected only 2/3 as much final product.
The problem:
While freeze precipitation worked perfectly for the first few jars of naphtha, for some reason the last few jars of the stuff yielded nothing when put into the freezer, despite being just as golden-colored as the first few jars. I cannot figure out why this would be! I tried adding some of the dried DMT freebase as a 'seed', as one would do with some crystals, with no result. I also eliminated a fair measure of the naphtha in one of the jars via plain old evaporation, but though the color of the solution got deeper and more vibrant, still nothing would precipitate out.
So could anybody perhaps venture a guess as to what might be causing freeze precipitation to fail? I checked the temperature of the freezer, and it was just as low as it had been for the initial few jars where the freeze precip worked great. Freeze precipitation is based on a very well-understood and simple process, that being the large difference in the solubility of DMT in naphtha as the temperature drops from warm, roughly 30 °C to almost -20 °C in this case. As the solubility of the stuff in naphtha drops with the temperature, the solution becomes supersaturated, causing some of the product to (slowly) crash out of solution. The process is so basic and fundamental that I can't figure out what the reason would be that it wouldn't work! Can anybody help me out with solving this mystery?
The options I have thought of as workarounds:
1. Further evaporate the naphtha. This leads me to ask the question of how DMT reacts to heat. Would it break down if I were to use a lab-grade hotplate to heat up the solution to aid in the evaporation? Is there a temperature above which the product will break down? Naphtha such as I have used boils somewhere between 30 and 90 °C, so considering that large range I can't predict specifically how hot it will have to be to boil, so instead of asking whether DMT is safe at a given temp (whatever the boiling point of my naphtha turns out to be), I'll ask if there's a limit to how high the temp can be allowed to go before degradation takes place.
2. Crashing out as a salt. I'm familiar with the fact that the DMT hemifumarate (one fumaric acid ion will bond to two ions of DMT) salt is for all intents and purposes insoluble in acetone, especially if you first saturate the acetone with fumaric acid, while freebase DMT and fumaric acid themselves are soluble in acetone. Fumaric acid is not soluble in naphtha, so you can't just crash the DMT out as hemifumarate from naphtha directly, but acetone and naphtha are themselves miscible. This leads me to wonder if it would work to saturate your acetone with fumaric acid, then add to naphtha/DMT solution. If the DMT and fumaric acid were then able to meet, the resulting salt would be insoluble in either the naphtha or the acetone, allowing it to precipitate out. This would be intended as a workaround for the lack of solubility of fumaric acid in naphtha itself.
However, I have no idea if saturating the acetone with fumaric acid and then adding to the DMT in naphtha solution would result in the salt or whether it would just further dilute the solution, with the fumaric acid becoming a contaminant, as my chemistry knowledge doesn't go that deep. Anybody have a better understanding of the concepts that underlie this theory?
In summary:
1. Does anybody have a clue why freeze precip would work beautifully for the first half of a batch of DMT in naphtha and yet not work for the second half?
2. Is DMT freebase sensitive to heat? Or better put since everything is ultimately sensitive to heat if the temp is high enough, at what temperature does DMT begin to degrade? This is pertinent to evaporating the naphtha solvent using a hot plate with teflon stir-bar.
3. Acetone and naphtha are miscible. DMT freebase is soluble in both solvents. Fumaric acid is mildly soluble in acetone, but not naphtha, and DMT hemifumarate is insoluble in both naphtha and for practical purposes, acetone. Thus could you precipitate out DMT hemifumarate from naphtha by adding fumaric acid saturated acetone dropwise, thus getting around the lack of solubility for fumaric acid in naphtha alone?
4. Any other ideas for either determining why freeze precipitation stopped working/for getting the goods out of naphtha besides the aforementioned evaporation or theoretical idea to crash out the fumarate? I'm down with getting it out as base or as a salt, as the salt can be subsequently liberated to base, but would prefer not to have to extract to aqueous solution as water is harder to evap than naphtha anyway.
Any help would be ultimate awesomeness and very much appreciated!
Thanks
D
EDIT:
To clarify, the contents of all the precipitation jars was homogenous prior to successfully precipitating from some of them. In other words the amount of DMT solute per volume of solvent was basically identical in all jars. This is why it confused me that the first few jars did precip properly and the last few did not.
It's also worth mentioning that when the unsuccessful precip jars are chilled to their proper temperature, they become massively hazy, to the point of being opaque. This seems to indicate that perhaps the precipitation is actually happening, but that the size of the resulting solids is so small that they are staying suspended in the naphtha rather than settling to the bottom.
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