Detection of Designer Anabolic Steroids by LC‐MS/MS and Commercial Synthesis of Oxandrolone

Abstract

As of late, the abuse of previously unknown steroids by professional and amateur athletes has become a major concern for athletic governing bodies. In order to detect designer steroids, which have been synthesized specifically to evade current analytical techniques, new analytical screening methods must be devised. For liquid chromatography‐tandem mass spectrometry at high collision energy, a precursor ion scan method was proposed, which allows for the detection of potential steroid analytes. The simultaneous presence of three specific fragmentation ions at m/z 105, 91, and 77 on an MS spectrum indicates a possible steroid molecule is present in the sample matrix. In addition to detection, a more efficient commercial‐grade synthesis was investigated regarding the anabolic steroid, oxandrolone. The Searle procedure was used as a starting point, for which new reagents were proposed to generate specific reaction intermediates: α‐bromoketone, enone, and hydroperoxide. Perbromides were used in place of molecular bromine to brominate the A ring, and an ozonolysis process was used in place of toxic reagents to oxidize the enone. Together, these mechanistic steps significantly increased the initial yield from 8% to 45%. At present, there is a constant battle between those synthesizing designer steroids to evade detection and those developing analytic techniques able to identify previously unknown steroids.