title: 6alpha-Methylandrostenedione: gas chromatographic mass spectrometric detection in doping control.
abstract: In recent years products containing 6alpha-methylandrost-4-ene-3,17-dione have appeared on the sport supplement market. Scientific studies have proven aromatase inhibition and anabolic and mild androgenic properties; however, no preparation has been approved for medical use up to now. In sports 6alpha-methylandrost-4-ene-3,17-dione has to be classified as a prohibited substance according to the regulations of the World Anti-Doping Agency (WADA). For the detection of its misuse the metabolism was studied following the administration of two preparations obtained from the Internet (Formadrol and Methyl-1-Pro). Several metabolites as well as the parent compounds were synthesized and the structures of 3alpha-hydroxy-6alpha-methyl-5beta-androstan-17-one, 6alpha-methylandrost-4-ene-3,17-dione, and 5beta-dihydromedroxyprogesterone were confirmed by nuclear magnetic resonance (NMR) spectroscopy. The main metabolite, 3alpha-hydroxy-6alpha-methyl-5beta-androstan-17-one, was found to be excreted as glucuronide and was still detectable in microg/mL amounts until urine collection was terminated (after 25 h). Additionally, samples from routine human sports doping control had already tested positive for the presence of metabolites of 6alpha-methylandrost-4-ene-3,17-dione. Screening analysis can be easily performed by the existing screening procedure for anabolic steroids using 3alpha-hydroxy-6alpha-methyl-5beta-androstan-17-one as target substance (limit of detection <10 ng/mL). Its discrimination from the closely eluting drostanolone metabolite, 3alpha-hydroxy-2alpha-methyl-5alpha-androstan-17-one, is possible as the mono-TMS derivative.
authors.affiliation: Center for Preventive Doping Research, Institute of Biochemistry, German Sport University Cologne, Cologne, Germany. m.parr@biochem.dshs-koeln.de
authors.forename: Maria K
authors.initials: MK
authors.lastname: Parr
authors.forename: Rymantas
authors.initials: R
authors.lastname: Kazlauskas
authors.forename: Nils
authors.initials: N
authors.lastname: Schlörer
authors.forename: Georg
authors.initials: G
authors.lastname: Opfermann
authors.forename: Thomas
authors.initials: T
authors.lastname: Piper
authors.forename: Gabriele
authors.initials: G
authors.lastname: Schulze
authors.forename: Wilhelm
authors.initials: W
authors.lastname: Schänzer
mesh_terms: D000328:Adult; D004300:Doping in Sports / Q000517:prevention & control*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006801:Humans; D008297:Male; D008777:Methyltestosterone / Q000652:urine*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D015813:Substance Abuse Detection / Q000379:methods*; D016482:Urinalysis / Q000379:methods*
chemical_list: D008777:Methyltestosterone