de Boer D, de Jong E G, Maes R A
Netherlands Institute for Drugs and Doping Research, University of Utrecht.
J Anal Toxicol. 1992 Jan-Feb;16(1):14-8. doi: 10.1093/jat/16.1.14.
The use of anabolic steroids and related compounds in sport is forbidden by the International Olympic Committee (IOC). Because danazol (17 alpha-pregna-2,4-dien-20-yno[2,3-D] isoxazol-17 beta-ol) is structurally related to the anabolic steroid stanozolol, its use should be questioned. Therefore, the detection and the significance of danazol in doping analysis are discussed. A urine specimen suspected of containing danazol metabolites was analyzed in order to characterize the metabolites. After isolation and conversion into three different derivatives, the metabolites were subjected to gas chromatography/mass spectrometry (GC/MS) in the electron impact (EI) mode. The structure assignment was based on the molecular ions, fragmentation patterns observed for the three different derivatives, and the possible metabolite structures given in the literature. Ethisterone was identified as a nonconjugated metabolite. 2-Hydroxymethylethisterone was observed in two stereoisomeric forms. One stereoisomer was found mainly in the nonconjugated steroid fraction and the other in the conjugated fraction. The results were confirmed by analyzing urine specimens of a volunteer who was known to have taken danazol. Derivatization methods and GC/MS data are given to implement danazol detection in routine screening and confirmation procedures.
国际奥委会（IOC）禁止在体育运动中使用合成代谢类固醇及相关化合物。由于达那唑（17α-孕甾-2,4-二烯-20-炔诺[2,3-D]异恶唑-17β-醇）在结构上与合成代谢类固醇司坦唑醇相关，其使用情况值得质疑。因此，本文讨论了达那唑在兴奋剂检测中的发现及意义。为了鉴定代谢物，对一份怀疑含有达那唑代谢物的尿液样本进行了分析。在将代谢物分离并转化为三种不同的衍生物后，采用电子轰击（EI）模式对其进行气相色谱/质谱联用（GC/MS）分析。结构鉴定基于分子离子、三种不同衍生物观察到的裂解模式以及文献中给出的可能的代谢物结构。炔诺酮被鉴定为一种非结合代谢物。观察到2-羟甲基炔诺酮有两种立体异构体形式。一种立体异构体主要存在于非结合类固醇组分中，另一种存在于结合组分中。通过分析一名已知服用过达那唑的志愿者的尿液样本，证实了上述结果。文中给出了衍生化方法和GC/MS数据，以用于在常规筛查和确认程序中进行达那唑检测。
