title: The synthesis and characterisation of MDMA derived from a catalytic oxidation of material isolated from black pepper reveals potential route specific impurities.
abstract: This work examines the chemical synthesis of 3,4-methylenedioxy-N-methylamphetamine (MDMA) from piperonal prepared via a catalytic ruthenium tetroxide oxidation of piperine extracted from black pepper. A variety of oxidation conditions were experimented with including different solvent systems and co-oxidants. A sample of prepared piperonal was successfully converted into MDMA via 3,4-methylenedioxyphenyl-2-nitropropene (MDP2NP) and 3,4-methylenedioxyphenyl-2-propanone (MDP2P) and the impurities within each product characterised by GC-MS to give a contaminant profile of the synthetic pathway. Interestingly, it was discovered that a chlorinated analogue of piperonal (6-chloropiperonal) was created during the oxidation process by an as yet unknown mechanism. This impurity reacted alongside piperonal to give chlorinated analogues of each precursor, ultimately yielding 2-chloro-4,5-methylenedioxymethamphetamine (6-Cl-MDMA) as an impurity within the MDMA sample. The methodology developed is a simple way to synthesise a substantial amount of precursor material with easy to obtain reagents. The results also show that chlorinated MDMA analogues, previously thought to be deliberately included adulterants, may in fact be route specific impurities with potential application in determining the origin and synthesis method of seized illicit drugs.
authors.affiliation: Australian Centre for Research on Separation Science (ACROSS), School of Science, RMIT University, GPO Box 2476, Melbourne, Victoria 3001, Australia.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Plummer
authors.affiliation: Australian Centre for Research on Separation Science (ACROSS), School of Science, RMIT University, GPO Box 2476, Melbourne, Victoria 3001, Australia.
authors.forename: Thomas W
authors.initials: TW
authors.lastname: Breadon
authors.affiliation: Victoria Police Forensic Services Centre, Macleod, Victoria 3085, Australia.
authors.forename: James R
authors.initials: JR
authors.lastname: Pearson
authors.affiliation: Australian Centre for Research on Separation Science (ACROSS), School of Science, RMIT University, GPO Box 2476, Melbourne, Victoria 3001, Australia. Electronic address: oliver.jones@rmit.edu.au.
authors.forename: Oliver A H
authors.initials: OAH
authors.lastname: Jones
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry; D052117:Benzodioxoles / Q000737:chemistry; D004340:Drug Contamination; D006213:Hallucinogens / Q000138:chemical synthesis*; D006801:Humans; D013287:Illicit Drugs / Q000737:chemistry*; D018817:N-Methyl-3,4-methylenedioxyamphetamine / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D029222:Piper nigrum / Q000737:chemistry*
chemical_list: D001547:Benzaldehydes; D052117:Benzodioxoles; D006213:Hallucinogens; D013287:Illicit Drugs; C005454:piperonal; D018817:N-Methyl-3,4-methylenedioxyamphetamine
keywords: Clandestine synthesis; MDMA; Pepper; Route specific impurities; Ruthenium tetroxide