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DMT and Dichloromethane: Rearrangement of quaternary ammonium salt

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Anthimus

Anthimus

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www.ncbi.nlm.nih.gov

N,N-Dimethyltryptamine and dichloromethane: rearrangement of quaternary ammonium salt product during GC-EI and CI-MS-MS analysis - PubMed

N,N-Dimethyltryptamine (DMT) 1 is a simple tryptamine derivative with powerful psychoactive properties. It is abundant in nature and easily accessible through a variety of synthetic routes. Most work-up procedures require the use of organic solvents and halogenated representatives are often...
www.ncbi.nlm.nih.gov www.ncbi.nlm.nih.gov

N,N-Dimethyltryptamine (DMT) 1 is a simple tryptamine derivative with powerful psychoactive properties. It is abundant in nature and easily accessible through a variety of synthetic routes. Most work-up procedures require the use of organic solvents and halogenated representatives are often employed. DMT was found to be reactive towards dichloromethane, either during work-up or long term storage therein, which led to the formation of the quaternary ammonium salt N-chloromethyl-DMT chloride 2. Analysis of this side-product by gas chromatography ion trap mass spectrometry (GC-MS), both in electron and chemical ionisation tandem MS modes, gave only degradation products. For example, 2 could not be detected but appeared to have rearranged to 3-(2-chloroethyl)indole 3 and 2-methyltetrahydro-beta-carboline 4, whereas HPLC analysis enabled the detection of 2. GC-MS is a standard tool for the fingerprinting of drug products. The identification of a particular synthetic route is based on the analysis of impurities, provided these side products can be established to be route-specific. The in situ detection of both 3 and 4 within a DMT sample may have led to erroneous conclusions with regards to the identification of the synthetic route.
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This study can be downloaded freely here.

It was observed that when DMT free base was left in DCM over a period of up to several days, crystalline needles pre-cipitated which were characterised as N -chloromethyl-DMT 2. Interestingly, it has also recently been shown by Buchanan andco-workers that 2 was indeed present as a side-product duringthe isolation of tryptamines from the Chinese shrub Acacia con- fusa. In that case, DCM had been used during the purificationof the plant extract[16]. A second example was found in the lit- erature where the N 1-methyl derivative of 2 was detected when N 1-Me-DMT was dissolved in DCM and irradiated at 253.7nmin the presence of pyridine N -oxide and benzophenone
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this is important considering DCM for extraction/purification makes it way into discussion here like a revolving door. it's too bad we don't have immediate access to more advanced analysis procedures.
 
..all samples of oz species tested carefully by endlessness in the acacia analysis thread were done with dcm, including up to two weeks sitting in solution and heat, and there was not even a trace of aforementioned by-product..

i think most solvents, in certain conditions, could react..

also remember, most lab grade solvents are still sold as 98%-99% pure..there can be trace products of long term storage (years or more in storage for instance)

btw, chloroform is known to react easily and create byproducts..
 
Sister wouldn't be in such a hurry to discount this paper's findings out of hand.

If endlessness ran NMR on the DCM from an acacia extraction, would the chlorinated product even show up? The paper above implies it would not be soluble in DCM, and would have fallen out of solution. Its also very possible, due to the trace amounts of alkaloids in acacia to begin with, that any precipitated chlorinated product might have been overlooked by Endlessness.

Sister has also seen similar references over the years and would suggest that using DCM for a quick extraction would be fine, but prolonged exposure to it should be avoided. But as DCM is not very selective it wouldn't be Sister's first choice as an extraction solvent anyway.
 
Brandt wrote three articles on this topic. My takeaway is don't let DMT sit in DCM "up to several days".

Characterization of the synthesis of N,N-dimethyltryptamine by reductive amination using gas chromatography ion trap mass spectrometry
Simon D. Brandt, Sharon A. Moore1, Sally Freeman2, Abu B. Kanu3

N,N-Dimethyltryptamine and dichloromethane: Rearrangement of quaternary ammonium salt product during GC–EI and CI-MS–MS analysis
Simon D. Brandt, Cláudia P.B. Martinsb, Sally Freemanc, Nicola Dempstera, Mark Wainwrighta, Philip G. Ribya and John F. Alderb

Halogenated solvent interactions with N,N-dimethyltryptamine: Formation of quaternary ammonium salts and their artificially induced rearrangements during analysis
Simon D. Brandt, Cláudia P.B. Martinsb, Sally Freemanc, Nicola Dempstera, 1, Philip G. Ribya, 1, Jochen Gartzd and John F. Alderb


Dr_Sister, extracting with DCM and recrystallization with heptane and the "problem of un-selectivity" is solved ! I think.

The density of DCM is a beautiful thing.
 
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