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.

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