Simultaneous analysis of six novel hallucinogenic (tetrahydrobenzodifuranyl)aminoalkanes (FLYs) and (benzodifuranyl)aminoalkanes (DragonFLYs) by GC-MS, LC-MS, and LC-MS-MS

Six novel hallucinogens classed as (tetrahydrobenzodifuranyl) aminoalkanes or (benzodifuranyl)aminoalkanes, which are known by the common names of FLY and DragonFLY, respectively, were synthesized. These compounds were simultaneously analyzed by gas chromatography (GC)-mass spectrometry (MS), liquid chromatography (LC)-MS, and LC-MS-MS. GCMS analysis of their free bases was not satisfactory for both mass spectral and chromatographic measurements, and thus trifluoroacetyl (TFA) derivatization was employed. However, it was found that the usual TFA derivatization procedure using trifluoroacetic anhydride caused dehydrogenation of FLYs to the corresponding DragonFLYs. Therefore, TFA derivatization of FLYs was reinvestigated; the presence of triethylamine could almost inhibit such dehydrogenation. LC separation of the analytes was successfully achieved by using a phenyl-type semimicro column with methanol gradient elution, while 1-(8-bromo-2,3,6,7-tetrahydrobenzo[1,2-b;4,5-b']difuran-4-yl)-2-methylaminopropane (N-methyl-DOB-FLY) and 1-(8-bromo-2,3,6,7-tetrahydrobenzo[1,2-b;4,5-b']difuran-4-yl)-2-aminopropane (DOB-FLY) were not separated on an octadecylsilica (ODS)-type column. Specific product ion spectra for all compounds were also obtained using LC-MS-MS, which enabled sensitive and reliable identification.