Steroidal isomers with uniform mass spectra of their per-TMS derivatives : synthesis of 17-hydroxyandrostan-3-ones, androst-1-, and -4-ene-3,17-diols

Titel in Übersetzung: Steroide Isomere mit einheitlichen Massenspektra ihrer per-TMS-Derivate : Synthese von 17-hydroxyandrostan-3-ones, androst-1-, und -4-ene-3,17-diols

Maria Kristina Parr, Josef Zapp, Michael Becker, Georg Opfermann, Ulrike Bartz, Wilhelm Schänzer

Publikation: Beitrag in FachzeitschriftZeitschriftenaufsätzeForschungBegutachtung

Abstract

In human sports doping control analysis most of the steroids are analyzed after enzymatic hydrolysis of the glucuronides as per-trimethylsilyl (TMS) derivatives applying gas chromatography–mass spectrometry (GC–MS). According to the recommendations of the World Anti-Doping Agency the identification of analytes should be based on retention time and on mass spectrometric characterization. This study shows that the bis-TMS derivatives of 16 specific C19 steroids, namely the stereoisomers of 5ξ-androst-1-ene-3ξ,17ξ-diol (8 isomers), androst-4-ene-3ξ,17ξ-diol (4 isomers), and 17ξ-hydroxy-5ξ-androstan-3-one (4 isomers), reveal very similar mass spectra. As a rule, when taking the retention times, which are provided as Kovac indices for all these isomers, into account, a restriction to two or three possible isomers is possible. Reliable identification should additionally include a comparison of the retention times of the analytes with the reference compounds measured concomitantly. In some cases standard addition may be appropriate. / Due to the limited availability, the above mentioned isomers were synthesized by reduction of the corresponding α,β-unsaturated oxo steroids either with K-Selectride or by catalytic hydrogenation (Pd/C as catalyst). The products of the reactions were identified by means of nuclear magnetic resonance (NMR) characterization and by further reduction to the corresponding 5ξ-androstane-3ξ,17ξ-diols and GC–MS comparison with commercially available reference standards. Verf.-Referat
Titel in ÜbersetzungSteroide Isomere mit einheitlichen Massenspektra ihrer per-TMS-Derivate : Synthese von 17-hydroxyandrostan-3-ones, androst-1-, und -4-ene-3,17-diols
OriginalspracheEnglisch
ZeitschriftSteroids
Jahrgang72
Seiten (von - bis)545-551
Seitenumfang7
ISSN0039-128x
PublikationsstatusVeröffentlicht - 2007

Fachgebiete und Schlagwörter

  • Biochemie
  • Doping
  • Dopinganalyse
  • Dopingbekämpfung
  • Dopingkontrolle
  • Dopingnachweis
  • Gaschromatographie
  • Massenspektrometrie
  • Sportmedizin
  • Steroid
  • Testverfahren

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