Methylnortestosterone is a progestin and synthetic androgenic anabolic steroid, prohibited by WADA. Methylnortestosterone misuse is commonly detected by monitoring the parent compound and its main metabolites, 17α‐methyl‐5α‐estrane‐3α, 17β‐diol (M1) and 17α‐methyl‐5β‐estrane‐3α, 17β‐diol (M2), in the glucuronide fraction. In the current study, a direct detection of methylnortestosterone sulfo‐conjugated metabolites after ethyl acetate extraction and analysis by LC/Q/TOF‐MS in negative ionization mode was performed, detecting two main sulfate metabolites (S1, S2). For the characterization of metabolites, samples from the excretion study, were additionally analyzed by GC–MS, after solvolysis and per TMS derivatization. RT and MS data collected, were compared with RT and MS data from metabolites of 17z‐methyl‐5α/β‐estrane‐3α/β, 17z‐diols structures with prefixed stereochemistry at 3 and 5 positions, synthesized through Grignard reaction from 19‐noretiocholanolone, 19‐norandrosterone and 19‐norepiandrosterone. Confirmed sulfate metabolites were S1, 17α‐methyl‐5α‐estrane‐3α, 17β‐diol 3α sulfate (detected up to 72 h) and S2, 17α‐methyl‐5β‐estrane‐3α, 17β‐diol 3α sulfate (detected up to 192 h).

中文翻译：

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人类尿液中甲基去甲睾酮滥用的替代标志物。

甲基去甲睾酮是一种孕激素和合成雄激素合成代谢类固醇，被世界反兴奋剂机构禁止。通常通过监测母体化合物及其主要代谢物 17α-甲基-5α-雌酮-3α、17β-二醇 (M1) 和 17α-甲基-5β-雌二醇 (M2) 和 17α-甲基-5β-雌二醇 (M2) 来检测甲基去甲睾酮滥用。葡糖苷酸部分。在目前的研究中，在乙酸乙酯萃取后直接检测甲基去甲睾酮磺基共轭代谢物，并在负电离模式下通过 LC/Q/TOF-MS 进行分析，检测两种主要的硫酸盐代谢物（S1、S2）。对于代谢物的表征，来自排泄研究的样品在溶剂分解和每个 TMS 衍生化后通过 GC-MS 进行额外分析。收集的 RT 和 MS 数据与来自 17z-methyl-5α/β-estrane-3α/β 代谢物的 RT 和 MS 数据进行比较，在 3 位和 5 位具有前缀立体化学的 17z-二醇结构，通过格氏反应从 19-去甲胆甾酮、19-去甲雄酮和 19-去甲雄酮合成。经证实的硫酸盐代谢物为 S1、17α-甲基-5α-雌二醇-3α、17β-二醇 3α 硫酸盐（检测时间长达 72 小时）和 S2、17α-甲基-5β-雌二醇-3α、17β-二醇 3α 硫酸盐（检测时间长达 72 小时） 192 小时）。