androst-5-en-17-on-3β-yl picolinate

• 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: androst-5-en-17-on-3β-yl picolinate
• 英文别名: DHEA-PI；[(3S,8R,9S,10R,13S,14S)-10,13-dimethyl-17-oxo-1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-3-yl] pyridine-2-carboxylate
• 化学式: C₂₅H₃₁NO₃
• 分子量: 393.526
• InChiKey: DNRACZKJJHERCS-DFRSGRCKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  56.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-吡啶甲酸 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 androst-5-en-17-on-3β-yl picolinate
  参考文献：
  名称：

  Synthesis of pyridine-carboxylate derivatives of hydroxysteroids for liquid chromatography–electrospray ionization-mass spectrometry

  摘要：

  Synthesis and liquid chromatography-electrospray ionization-mass spectrometric (LC-ESI-MS) behaviors of the picolinoyl, 6-methylpicolinoyl, nicotinoyl, 2-methoxynicotinoyl and isonicotinoyl derivatives of the hydroxysteroids estrone, estradiol, 3 beta-hydroxyandrost-5en-17-one (dehydroepiandrosterone) and testosterone in positive mode were investigated. Each steroid was converted to the corresponding pyridine-carboxylate derivative by the acyl chloride method or the mixed anhydride method using the corresponding free acids and 2-methyl-6-nitrobenzoic anhydride; in each case, the latter method principally gave a better yield. The pyridine-carboxylate derivative of each steroid exhibited a clear single peak in liquid chromatography with a reversed phase column and CH3CN-0.1% CH3COOH as a mobile phase. The positive-ESI-mass spectra of the picolinoyl, 6-methylpicolinoyl and 2-methoxynicotinoyl derivatives showed a predominance of [M+H](+), whereas [M+H+CH3CN](+) was observed with high intensity in the nicotinoyl and isonicotinoyl derivatives. Even in the case of estradiol, with its two hydroxyl groups, a single charged ion of [M+H](+) or [M+H+CH3CN](+) was observed in the positive-ESI-mass spectrum of each derivative. The results revealed that picolinoyl derivatization is a simple and versatile method suitable for the sensitive and specific determination of hydroxysteroids by LC-ESI-MS (selected reaction monitoring). (c) 2006 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2006.10.005

文献信息

• Simultaneous quantitation of nine hydroxy-androgens and their conjugates in human serum by stable isotope dilution liquid chromatography electrospray ionization tandem mass spectrometry
  作者：Tianzhu Zang、Daniel Tamae、Clementina Mesaros、Qingqing Wang、Meng Huang、Ian A. Blair、Trevor M. Penning

  DOI：10.1016/j.jsbmb.2016.08.001

  日期：2017.1

  direct detection of steroid conjugates by electrospray-ionization tandem mass spectrometry has advantages the detection of unconjugated and conjugated steroids would require separate methods for each set of analytes. Our method was applied to pooled serum from male and female donors to provide reference values for both unconjugated and conjugated hydroxy-androgens. This method will allow us to interrogate

  去势抵抗性前列腺癌 (CRPC) 是前列腺癌的致命形式，尽管循环睾酮 (T) 和 5α-二氢睾酮 (DHT) 的去势水平仍然依赖于雄激素。为了研究肿瘤合成自身雄激素并对醋酸阿比特龙和恩杂鲁胺产生耐药性的机制，测量完整雄激素谱的方法势在必行。在此，我们报告了稳定同位素稀释液相色谱电喷雾电离串联质谱 (SID-LC-ESI-MS/MS) 方法的开发和验证，该方法可量化九种人羟基雄激素（吡啶甲酸），同时具有必要的特异性和灵敏度。在所建立的方法中，鉴定了所有九种羟基雄激素吡啶甲酸酯的碎片模式，并使用[13C3]-5α-雄甾烷-3α，17β-二醇和[13C3]-5α-雄甾烷-3β，17β-二醇作为内标是通过酶法合成的。日内和日间精密度和准确度符合美国食品和药物管理局生物分析方法验证标准。九种羟基雄激素的定量下限 (LLOQ) 为柱上 1.0pg 至 2.5pg。不常测量的二醇：5-雄烯-3β、17β-二醇和
• Fusaric acid as a novel proton-affinitive derivatizing reagent for highly sensitive quantification of hydroxysteroids by LC-ESI-MS/MS
  作者：Kouwa Yamashita、Keiko Yamazaki、Sachiko Komatsu、Mitsuteru Numazawa

  DOI：10.1016/j.jasms.2009.10.008

  日期：2010.2.1

  A highly sensitive derivatization method for liquid chromatography (LC)-electrospray ionization (ESI) tandem mass spectrometry of dehydroepiandrosterone (DHEA), testosterone (T), pregnenolone (P5), and 17α-OH-pregnenolone (17-OHP5) was developed based on the use of fusaric acid as a reagent. DHEA, P5, and 17-OHP5 were rapidly and quantitatively converted to the 3-fusarate esters by treatment with fusaric acid and 2-methyl-6-nitrobenzoic anhydride. The positive ESI-mass spectra of the fusarate esters of each steroid were dominated by the appearance of [M + H]+ as base peaks. The fusarate derivatization of these steroids showed 17.6-fold (DHEA), 11.9-fold (P5), 3.3-fold (17-OHP5), and 1.8-fold (T) higher sensitivity to those of the corresponding picolinate derivatives in LC-selected reaction monitoring.

  一种高灵敏度的衍生化方法被开发用于液相色谱（LC）-电喷雾离子化（ESI）串联质谱，针对脱氢表雄酮（DHEA）、睾酮（T）、孕烯醇酮（P5）和17α-羟基孕烯醇酮（17-OHP5），该方法基于使用葫芦酸作为试剂。DHEA、P5和17-OHP5经过葫芦酸和2-甲基-6-硝基苯甲酸酐处理后迅速且定量地转化为3-葫芦酸酯。每种类固醇的葫芦酸酯的正离子电喷雾质谱以[M + H]+为基峰。与相应的吡咯啉衍生物相比，这些类固醇的葫芦酸衍生化在LC选择反应监测中表现出17.6倍（DHEA）、11.9倍（P5）、3.3倍（17-OHP5）和1.8倍（T）更高的灵敏度。