mikeAtHome
The only God I can imagine is a God that I can't p
Hi all.
I’ve just read a mind-blowing article about the DMT molecule that I wanted to share with you. I’ll summarize the findings and try to explain what certain procedures mean to save you time from having to read the entire article yourself and then research what certain sections mean. But first, I’m going to provide a preamble and if you get bored reading it then just jump right to the source (and spend even more time dealing with that). But here it is in case you want:
“Investigations into the polymorphic properties of N,N-dimethyltryptamine by X-ray diffraction and differential scanning calorimetry”
(this link works for me but I don’t know if it’s because I created an account or not, I can’t remember. If I did need to create an account, I guarantee that its free or I wouldn’t have done it.)
First, I need to come clean. I am a new member here and got most of my practical chem knowledge from the abundance of meth forums on the Internet. I spent a long time and never talked to a soul. Not because I’m shy, because all the threads and info were over 10 years old (more like 15). Nobody in the USA makes meth any more except for a few hobbyists and those able to steal lab supplies. If you look on the dark web, there are a good number of meth sellers but I’m pretty sure all that stuff is coming in via Mexico.
Meth chemistry is very interesting, especially as it developed over the years. There were tons of ways to synthesize it from easily obtainable sources. Then chemicals started getting regulated which drove down the number of reductions available. Towards the end of the meth craze (around 2003-2004) most folks were using OTC allergy meds as their precursors and doing reductions in one of 2 ways. What is interesting is in the way home chemists had to constantly keep up with new junk manufacturers were putting in their pills to prevent the isolation of the precursors. So you would wind up having to do many extractions before you could reduce and then extract your product from the freebase that the reduction left you with. The extractions were mainly targeted at pulling out contaminants. Some extractions were to extract precursors that would be used to create precursors that you needed for the ultimate reduction. It got very interesting.
While DMT can be synthesized many ways, I don’t hear of them around here, only extractions of the natural product. That’s fine. Even if I could get my hands on the precursors I’m not nearly talented or brave enough to perform a messy synth. What struck me as odd when I came here was a perceived lack of drive to perfect these extractions. When meth started getting tough, I saw everyone scrambling to identify the latest contaminant and a way to target its elimination. Yields got very important. Here, yields from bark range from under 1% to over 5% - and that’s just for MHRB! And within those extractions that used the same tek on the same strain, there were all these different results: different colored spice, spice just melting away, emulsions and so on. And nobody seemed very interested in getting to the bottom of it. I even saw one post on another forum to a guy who had just done his first extraction, managing like 0.3gr from 50gr MHRB. He had no idea if that was good or bad and could have cared less. When someone posted some advice that could possibly increase his yield, his response was, something like, “nah, that’s okay, I like the way I’m doing it.” The DMT world is so laid back when it comes to perfecting yields that it was driving me crazy. Then I read this article and all became clear.
One last thing before the article summary. I probably shouldn’t even have an opinion on this because I’ve never even performed an extraction. But I felt from the beginning that hexane (and that’s not the same as heptane) might make an excellent solvent for STB (I also think STB makes way more sense than A/B but that’s another story and again, I don’t have enough experience to be committed to that opinion but think I could provide a reasonable defense for it). NAPTHA’s inability to commit to being a solvent unless it’s warm works to the advantage of A/B. Not so for STB. I did find some validation about hexane out there on at least one other forum. And still other forums trash talking NAPTHA in favor of toluene. Opinions abound. This article makes use of hexane in a STB and nothing terrible happens. So let’s get to it:
Some background terms:
“Amorphous/Polymorphous” molecular behavior, “DSC”, “Heat Capacity” (or Cp for short) and “Phase Shift.”
What “Polymorphous behavior” refers to is a compound's propensity of going from glass-like in structure to crystal-like (and back). The opposite behavior is “Amorphous” (compounds arrange their molecules in a particular pattern and stay that way). Phase Shifting is similar but refers only to the natural changes that happen to any element when it changes “phase” – liquid, solid and gas etc. We usually attribute phase change to changes in temperature. So if a compound is polymorphous then any particular sample of that compound can change phase (melt, crystalize, whatever) at a temperature that is different from other samples in the exact same compound!
As for the remaining unexplained terms:
“Differential Scanning Calorimetry, or DSC, is a thermal analysis technique that looks at how a material’s heat capacity (Cp) is changed by temperature. “ I.e. how much heat is required to raise a compound’s temperature and by implication the heat required for a phase change.
One of the article’s quotes might refer to a Fast Scan or Fast DSC. That’s just a DSC that changes a compound’s temperature very fast. They do this because it fast-tracks a polymorphous compound’s inclination to shift to a new phase.
Okay, here’s what these guys did.
Actions Taken
#1. They created samples of DMT by way of synthesis and plant extraction. The extracted DMT used hexane via STB .
#2. Then they ran two Fast DSC’s of varying temperatures. I think they stashed some samples away without running any DSC on them so they could experiment with other ways of getting a sample to have a particular polymorphous property that was not the result of a DSC. For the samples that did get a DSC, the DSC did cause a change in polymorphous behavior. But other things could also change that behavior as you’ll see. Polymorphous compounds are weird not only in that they do that glass/crystal thing but they also change in other particulars like Cp, melting point and even color. The bottom line is that the two DSC’s created two more divisions among the sample for the authors to observe with the primary difference being different melting points.
#3. They re-crystallized some samples using hexane and all other samples with a different solvent called acetonitrile. Again, a sample’s method of re-crystallization was independent of how the sample was treated in #1 or #2.
So you have 3 different treatments going on and any particular sample could be the result of any combination of those three treatments. What they saw after re-crystallization is that the DMT re-crystalized with hexane had white crystals and the other samples had yellow crystals. In other words, just using a different solvent for re-crystallization had an effect on at least on polymorphous property.
This was getting confusing but they finally decided to create three named binary categories for the samples:
“…samples W1 and W2 were predominantly white crystals obtained using crystallization from hexane; whereas yellow DMT samples Y1 and Y2 were obtained following crystallization with acetonitrile. Samples W1 and Y1 were crystallized from DMT prepared by organic synthesis, while samples W2 and Y2 were from DMT isolated from the bark of M. tenuiflora.”
And then:
“…the higher melting polymorph was deemed Form I whereas the lower melting polymorph was termed Form II.”
Here what they discovered and concluded: (I’m not bothering with the quotes because I’ve condensed and re-worded a little):
-The samples with the lowest melting point encountered were described as a pale amorphous solid that melted at 38 °C–40 °C. At the other end of the spectrum were samples with a melting point of 47 °C–49 °C following its synthesis and recrystallization from hexane. Interestingly, the authors then mentioned a conversion of this sample to a form with a higher melting point (71 °C–73 °C), also by recrystallization from hexane, by seeding with an authentic sample with a melting point of 73 °C–74 °C, respectively.
-They confirmed the prevalence of Form II in this sample compared with DMT W1 and that again it converted to Form I at the slower heating rates.
-They confirmed the apparent higher ratio of Form II in sample W2.
-The recrystallization to Form II in DMT W2 was not as easily accomplished as in DMT W1.
-One attempt to obtain pure Form 1 was by heating the untreated samples to 45 °C and holding the samples at this temperature for 20 min to allow conversion of the Form II in the sample to Form I, prior to cooling and then re-scanning at 2 °C min− 1. The approach indeed worked
-DMT Y1 and DMT Y2 were both yellow and appeared denser and less crystalline.
-DMT Y2 displayed an increased prevalence of Form I in the sample at 100 °C min− 1. Indeed, at 2 °C min− 1 there was little evidence for any melting or conversion from Form II to Form I.
-They confirmed that DMT Y2 initially was the most amorphous of the samples and contained the highest level in Form 1 of DMT.
-They were able to confirm the apparent instability of the Form II of DMT (those were the samples with the low melting point and hence judged instable, I suppose).
The data provided in this paper have shown that DMT can be recrystallized from the solvents hexane and acetonitrile to give crystals that are a mixture of two polymorphs. The fact that two clearly exist explains the variation in melting points reported previously in the literature. It seems possible that use of the latter solvent gives crystals with a greater amorphousness and a yellow coloration. This solvent dependency was independent of the source of DMT.
The data thus suggest that this was solvent-mediated through increased amorphicity in the sample rather than a specific solvent–DMT interaction.
The data provided in this paper have shown that DMT can be recrystallized from the solvents hexane and acetonitrile to give crystals that are a mixture of two polymorphs
One attempt to obtain pure Form 1 was by heating the untreated samples to 45 °C and holding the samples at this temperature for 20 min to allow conversion of the Form II in the sample to Form I, prior to cooling and then re-scanning at 2 °C min− 1. …this approach indeed worked …
And as for yellow DMT…
“...was solvent-mediated through increased amorphicity in the sample rather than a specific solvent–DMT interaction.”
Well that’s about it. DMT is a crazy molecule. I can’t change its mind about any particular property for just about any reason it wants. I’m not sure what the actionables are. If we don’t want a low/unstable melting point does that mean that we shouldn’t switch solvents midstream, or that we shouldn’t use acetonitrile to re-crystallize or that we should use hexane or none of the above?
I liked that last comment about the yellow crystals not being caused by the solvent but by a change to “amorphicity” brought on by the solvent. I've heard so much about mysterious yellow crystaks that seem to pop up out of nowhere in someone's extraction. The question has veen anwered: THERE IS NO ANSWER!
And that's why DMT laughs...
I’ve just read a mind-blowing article about the DMT molecule that I wanted to share with you. I’ll summarize the findings and try to explain what certain procedures mean to save you time from having to read the entire article yourself and then research what certain sections mean. But first, I’m going to provide a preamble and if you get bored reading it then just jump right to the source (and spend even more time dealing with that). But here it is in case you want:
“Investigations into the polymorphic properties of N,N-dimethyltryptamine by X-ray diffraction and differential scanning calorimetry”
(this link works for me but I don’t know if it’s because I created an account or not, I can’t remember. If I did need to create an account, I guarantee that its free or I wouldn’t have done it.)
First, I need to come clean. I am a new member here and got most of my practical chem knowledge from the abundance of meth forums on the Internet. I spent a long time and never talked to a soul. Not because I’m shy, because all the threads and info were over 10 years old (more like 15). Nobody in the USA makes meth any more except for a few hobbyists and those able to steal lab supplies. If you look on the dark web, there are a good number of meth sellers but I’m pretty sure all that stuff is coming in via Mexico.
Meth chemistry is very interesting, especially as it developed over the years. There were tons of ways to synthesize it from easily obtainable sources. Then chemicals started getting regulated which drove down the number of reductions available. Towards the end of the meth craze (around 2003-2004) most folks were using OTC allergy meds as their precursors and doing reductions in one of 2 ways. What is interesting is in the way home chemists had to constantly keep up with new junk manufacturers were putting in their pills to prevent the isolation of the precursors. So you would wind up having to do many extractions before you could reduce and then extract your product from the freebase that the reduction left you with. The extractions were mainly targeted at pulling out contaminants. Some extractions were to extract precursors that would be used to create precursors that you needed for the ultimate reduction. It got very interesting.
While DMT can be synthesized many ways, I don’t hear of them around here, only extractions of the natural product. That’s fine. Even if I could get my hands on the precursors I’m not nearly talented or brave enough to perform a messy synth. What struck me as odd when I came here was a perceived lack of drive to perfect these extractions. When meth started getting tough, I saw everyone scrambling to identify the latest contaminant and a way to target its elimination. Yields got very important. Here, yields from bark range from under 1% to over 5% - and that’s just for MHRB! And within those extractions that used the same tek on the same strain, there were all these different results: different colored spice, spice just melting away, emulsions and so on. And nobody seemed very interested in getting to the bottom of it. I even saw one post on another forum to a guy who had just done his first extraction, managing like 0.3gr from 50gr MHRB. He had no idea if that was good or bad and could have cared less. When someone posted some advice that could possibly increase his yield, his response was, something like, “nah, that’s okay, I like the way I’m doing it.” The DMT world is so laid back when it comes to perfecting yields that it was driving me crazy. Then I read this article and all became clear.
One last thing before the article summary. I probably shouldn’t even have an opinion on this because I’ve never even performed an extraction. But I felt from the beginning that hexane (and that’s not the same as heptane) might make an excellent solvent for STB (I also think STB makes way more sense than A/B but that’s another story and again, I don’t have enough experience to be committed to that opinion but think I could provide a reasonable defense for it). NAPTHA’s inability to commit to being a solvent unless it’s warm works to the advantage of A/B. Not so for STB. I did find some validation about hexane out there on at least one other forum. And still other forums trash talking NAPTHA in favor of toluene. Opinions abound. This article makes use of hexane in a STB and nothing terrible happens. So let’s get to it:
Some background terms:
“Amorphous/Polymorphous” molecular behavior, “DSC”, “Heat Capacity” (or Cp for short) and “Phase Shift.”
What “Polymorphous behavior” refers to is a compound's propensity of going from glass-like in structure to crystal-like (and back). The opposite behavior is “Amorphous” (compounds arrange their molecules in a particular pattern and stay that way). Phase Shifting is similar but refers only to the natural changes that happen to any element when it changes “phase” – liquid, solid and gas etc. We usually attribute phase change to changes in temperature. So if a compound is polymorphous then any particular sample of that compound can change phase (melt, crystalize, whatever) at a temperature that is different from other samples in the exact same compound!
As for the remaining unexplained terms:
“Differential Scanning Calorimetry, or DSC, is a thermal analysis technique that looks at how a material’s heat capacity (Cp) is changed by temperature. “ I.e. how much heat is required to raise a compound’s temperature and by implication the heat required for a phase change.
One of the article’s quotes might refer to a Fast Scan or Fast DSC. That’s just a DSC that changes a compound’s temperature very fast. They do this because it fast-tracks a polymorphous compound’s inclination to shift to a new phase.
Okay, here’s what these guys did.
Actions Taken
#1. They created samples of DMT by way of synthesis and plant extraction. The extracted DMT used hexane via STB .
#2. Then they ran two Fast DSC’s of varying temperatures. I think they stashed some samples away without running any DSC on them so they could experiment with other ways of getting a sample to have a particular polymorphous property that was not the result of a DSC. For the samples that did get a DSC, the DSC did cause a change in polymorphous behavior. But other things could also change that behavior as you’ll see. Polymorphous compounds are weird not only in that they do that glass/crystal thing but they also change in other particulars like Cp, melting point and even color. The bottom line is that the two DSC’s created two more divisions among the sample for the authors to observe with the primary difference being different melting points.
#3. They re-crystallized some samples using hexane and all other samples with a different solvent called acetonitrile. Again, a sample’s method of re-crystallization was independent of how the sample was treated in #1 or #2.
So you have 3 different treatments going on and any particular sample could be the result of any combination of those three treatments. What they saw after re-crystallization is that the DMT re-crystalized with hexane had white crystals and the other samples had yellow crystals. In other words, just using a different solvent for re-crystallization had an effect on at least on polymorphous property.
This was getting confusing but they finally decided to create three named binary categories for the samples:
“…samples W1 and W2 were predominantly white crystals obtained using crystallization from hexane; whereas yellow DMT samples Y1 and Y2 were obtained following crystallization with acetonitrile. Samples W1 and Y1 were crystallized from DMT prepared by organic synthesis, while samples W2 and Y2 were from DMT isolated from the bark of M. tenuiflora.”
And then:
“…the higher melting polymorph was deemed Form I whereas the lower melting polymorph was termed Form II.”
Here what they discovered and concluded: (I’m not bothering with the quotes because I’ve condensed and re-worded a little):
-The samples with the lowest melting point encountered were described as a pale amorphous solid that melted at 38 °C–40 °C. At the other end of the spectrum were samples with a melting point of 47 °C–49 °C following its synthesis and recrystallization from hexane. Interestingly, the authors then mentioned a conversion of this sample to a form with a higher melting point (71 °C–73 °C), also by recrystallization from hexane, by seeding with an authentic sample with a melting point of 73 °C–74 °C, respectively.
-They confirmed the prevalence of Form II in this sample compared with DMT W1 and that again it converted to Form I at the slower heating rates.
-They confirmed the apparent higher ratio of Form II in sample W2.
-The recrystallization to Form II in DMT W2 was not as easily accomplished as in DMT W1.
-One attempt to obtain pure Form 1 was by heating the untreated samples to 45 °C and holding the samples at this temperature for 20 min to allow conversion of the Form II in the sample to Form I, prior to cooling and then re-scanning at 2 °C min− 1. The approach indeed worked
-DMT Y1 and DMT Y2 were both yellow and appeared denser and less crystalline.
-DMT Y2 displayed an increased prevalence of Form I in the sample at 100 °C min− 1. Indeed, at 2 °C min− 1 there was little evidence for any melting or conversion from Form II to Form I.
-They confirmed that DMT Y2 initially was the most amorphous of the samples and contained the highest level in Form 1 of DMT.
-They were able to confirm the apparent instability of the Form II of DMT (those were the samples with the low melting point and hence judged instable, I suppose).
Conclusion
The data provided in this paper have shown that DMT can be recrystallized from the solvents hexane and acetonitrile to give crystals that are a mixture of two polymorphs. The fact that two clearly exist explains the variation in melting points reported previously in the literature. It seems possible that use of the latter solvent gives crystals with a greater amorphousness and a yellow coloration. This solvent dependency was independent of the source of DMT.
The data thus suggest that this was solvent-mediated through increased amorphicity in the sample rather than a specific solvent–DMT interaction.
The data provided in this paper have shown that DMT can be recrystallized from the solvents hexane and acetonitrile to give crystals that are a mixture of two polymorphs
One attempt to obtain pure Form 1 was by heating the untreated samples to 45 °C and holding the samples at this temperature for 20 min to allow conversion of the Form II in the sample to Form I, prior to cooling and then re-scanning at 2 °C min− 1. …this approach indeed worked …
And as for yellow DMT…
“...was solvent-mediated through increased amorphicity in the sample rather than a specific solvent–DMT interaction.”
Well that’s about it. DMT is a crazy molecule. I can’t change its mind about any particular property for just about any reason it wants. I’m not sure what the actionables are. If we don’t want a low/unstable melting point does that mean that we shouldn’t switch solvents midstream, or that we shouldn’t use acetonitrile to re-crystallize or that we should use hexane or none of the above?
I liked that last comment about the yellow crystals not being caused by the solvent but by a change to “amorphicity” brought on by the solvent. I've heard so much about mysterious yellow crystaks that seem to pop up out of nowhere in someone's extraction. The question has veen anwered: THERE IS NO ANSWER!
And that's why DMT laughs...