Analysis of non‐ketoic steroids 17α‐methylepithiostanol and desoxymethyl‐ testosterone in dietary supplements

Dietary supplements containing 17α‐methyl‐2,3‐epithio‐5α‐androstane‐17β‐ol (17α‐methylepithiostanol), which is a 17‐methylated analogue of epithiostanol or a prodrug of desoxymethyltestosterone (17α‐methyl‐5α‐androst‐2‐en‐17β‐ol), have recently appeared on the Internet. 17α‐Methylepithiostanol and desoxymethyltestosterone are classified as prohibited substances on the World Anti‐Doping Agency (WADA) list. Two preparations, EPISTANE™ and P‐PLEX™, were obtained from the Internet so that their contents could be investigated. This study involved gas chromatography/mass spectrometry (GC/MS) analysis after trimethylsilyl (TMS) derivatization, liquid chromatography/mass spectrometry (LC/MS) in atmospheric pressure photoionization (APPI) mode and nuclear magnetic resonance (NMR) spectroscopy. Analysis using LC/MS in APPI mode would be a useful tool for detecting heat‐labile and non‐polar steroids. Although the labelling of EPISTANE™ indicates that it contains 17α‐methyl‐2α, 3α‐epithio‐5α‐androstane‐17β‐ol only, 17α‐methyl‐2β,3β‐epithio‐5α‐androstane‐17β‐ol and desoxymethyltestosterone were identified in the supplement. The results showed that P‐PLEX™ contained desoxymethyltestosterone and its isomer 17α‐methyl‐5α‐androst‐3‐en‐17β‐ol. Urine samples can be screened after EPISTANE™ or P‐PLEX™ administration using the normal screening procedure for anabolic steroids with GC/MS. Copyright © 2009 John Wiley & Sons, Ltd.