Methyltestosterone M (5B-Androstan-17A-methyl-3A,17B-diol), TMS | 136693-16-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: Methyltestosterone M (5B-Androstan-17A-methyl-3A,17B-diol), TMS
• 英文别名: trimethyl-[[(3R,5R,8R,9S,10S,13S,14S,17S)-10,13,17-trimethyl-3-trimethylsilyloxy-1,2,3,4,5,6,7,8,9,11,12,14,15,16-tetradecahydrocyclopenta[a]phenanthren-17-yl]oxy]silane
• CAS: 136693-16-8
• 化学式: C₂₆H₅₀O₂Si₂
• 分子量: 450.853
• InChiKey: GNQZRHQPXWSWJC-VLHNWRQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  17α-methyl-5β-androstane-3α,17β-diol 3-sulfate 在 碘化铵 、 2-巯基乙醇 、 sodium hydroxide 作用下， 反应 0.66h， 生成 Methyltestosterone M (5B-Androstan-17A-methyl-3A,17B-diol), TMS
  参考文献：
  名称：

  Alternative long-term markers for the detection of methyltestosterone misuse

  摘要：

  Methyltestosterone (MT) is one of the most frequently detected anabolic androgenic steroids in doping control analysis. MT misuse is commonly detected by the identification of its two main metabolites excreted as glucuronide conjugates, 17 alpha-methyl-5 alpha-androstan-3 alpha,17 beta-diol and 17 alpha-methyl-5 beta-androstan-3 alpha,17 beta-diol. The detection of these metabolites is normally performed by gas chromatography-mass spectrometry, after previous hydrolysis with beta-glucuronidase enzymes, extraction and derivatization steps. The aim of the present work was to study the sulphate fraction of MT and to evaluate their potential to improve the detection of the misuse of the drug in sports. MT was administered to healthy volunteers and urine samples were collected up to 30 days after administration. After an extraction with ethyl acetate, urine extracts were analysed by liquid chromatography tandem mass spectrometry using electrospray ionisation in negative mode by monitoring the transition m/z 385 to m/z 97. Three diol sulphate metabolites (S1, S2 and S3) were detected. Potential structures for these metabolites were proposed after solvolysis and mass spectrometric experiments: S1, 17 alpha-methyl-5 beta-androstan-3 alpha,17 beta-diol 3 alpha-sulphate; S2, 17 beta-methyl-5 alpha-androstan-3 alpha,17 alpha-diol 3 alpha-sulphate; and S3, 17 beta-methyl-5 beta-androstan-3 alpha,17 alpha-diol 3 alpha-sulphate. Synthesis of reference compounds will be required in order to confirm the structures. The retrospectivity of these sulphate metabolites in the detection of MT misuse was compared with the obtained with previously described metabolites. Metabolite S2 was detected up to 21 days after MT administration, improving between 2 and 3 times the retrospectivity of the detection compared to the last long-term metabolite of MT previously described, 17 alpha-hydroxy-17 beta-methylandrostan-4,6-dien-3-one. (c) 2012 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2012.10.008

文献信息

• Mass spectrometric behavior of anabolic androgenic steroids using gas chromatography coupled to atmospheric pressure chemical ionization source. Part I: Ionization
  作者：M. Raro、T. Portolés、J. V. Sancho、E. Pitarch、F. Hernández、J. Marcos、R. Ventura、C. Gómez、J. Segura、O. J. Pozo

  DOI：10.1002/jms.3367

  日期：2014.6

  The detection of anabolic androgenic steroids (AAS) is one of the most important topics in doping control analysis. Gas chromatography coupled to (tandem) mass spectrometry (GC–MS(/MS)) with electron ionization and liquid chromatography coupled to tandem mass spectrometry have been traditionally applied for this purpose. However, both approaches still have important limitations, and, therefore, detection

  合成代谢雄激素类固醇（AAS）的检测是兴奋剂控制分析中最重要的主题之一。气相色谱联用电子电离（串联）质谱分析法（GC-MS（/ MS））和液相色谱联用的质谱联用已被传统地用于此目的。但是，这两种方法仍然具有重要的局限性，因此，目前通过这些策略的组合可以检测所有AAS。替代电离技术可以最大程度地减少这些缺点，并有助于实施一种用于检测AAS的单一方法。在当前工作中，已经测试了一种商业化的气相色谱与四极杆飞行时间分析仪结合使用的新型常压化学电离（APCI）源，以评估60型AAS的电离。已对未衍生化和三甲基甲硅烷基（TMS）衍生的化合物进行了研究。使用GC–APCI–MS可以将所有测定的AAS离子化，无论其结构如何。源中水作为改性剂的存在促进了质子化分子的形成（[M + H]+），成为大多数研究化合物的光谱基峰。在这些条件下，非衍生化AAS的[M + H] +，[M + H-H 2 O] +和[M
• MASSE, ROBERT;AYOTTE, CHRISTIANE;DUGAL, ROBERT, J. CHROMATOGR. BIOMED. APPL., 489,(1989) N, C. 23-50
  作者：MASSE, ROBERT、AYOTTE, CHRISTIANE、DUGAL, ROBERT

  DOI：——

  日期：——
• Alternative long-term markers for the detection of methyltestosterone misuse
  作者：C. Gómez、O.J. Pozo、J. Marcos、J. Segura、R. Ventura

  DOI：10.1016/j.steroids.2012.10.008

  日期：2013.1

  Methyltestosterone (MT) is one of the most frequently detected anabolic androgenic steroids in doping control analysis. MT misuse is commonly detected by the identification of its two main metabolites excreted as glucuronide conjugates, 17 alpha-methyl-5 alpha-androstan-3 alpha,17 beta-diol and 17 alpha-methyl-5 beta-androstan-3 alpha,17 beta-diol. The detection of these metabolites is normally performed by gas chromatography-mass spectrometry, after previous hydrolysis with beta-glucuronidase enzymes, extraction and derivatization steps. The aim of the present work was to study the sulphate fraction of MT and to evaluate their potential to improve the detection of the misuse of the drug in sports. MT was administered to healthy volunteers and urine samples were collected up to 30 days after administration. After an extraction with ethyl acetate, urine extracts were analysed by liquid chromatography tandem mass spectrometry using electrospray ionisation in negative mode by monitoring the transition m/z 385 to m/z 97. Three diol sulphate metabolites (S1, S2 and S3) were detected. Potential structures for these metabolites were proposed after solvolysis and mass spectrometric experiments: S1, 17 alpha-methyl-5 beta-androstan-3 alpha,17 beta-diol 3 alpha-sulphate; S2, 17 beta-methyl-5 alpha-androstan-3 alpha,17 alpha-diol 3 alpha-sulphate; and S3, 17 beta-methyl-5 beta-androstan-3 alpha,17 alpha-diol 3 alpha-sulphate. Synthesis of reference compounds will be required in order to confirm the structures. The retrospectivity of these sulphate metabolites in the detection of MT misuse was compared with the obtained with previously described metabolites. Metabolite S2 was detected up to 21 days after MT administration, improving between 2 and 3 times the retrospectivity of the detection compared to the last long-term metabolite of MT previously described, 17 alpha-hydroxy-17 beta-methylandrostan-4,6-dien-3-one. (c) 2012 Elsevier Inc. All rights reserved.