3,20-Bis-(O-methyloxim)-cortisol-trimethylsilyl-ether | 32221-26-4

• 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: 3,20-Bis-(O-methyloxim)-cortisol-trimethylsilyl-ether
• 英文别名: Pregn-4-ene-3,20-dione, 11,17,21-tris[(trimethylsilyl)oxy]-, bis(O-methyloxime), (11beta)-；(8S,9S,10R,11S,13S,14S,17R)-N-methoxy-17-[N-methoxy-C-(trimethylsilyloxymethyl)carbonimidoyl]-10,13-dimethyl-11,17-bis(trimethylsilyloxy)-2,6,7,8,9,11,12,14,15,16-decahydro-1H-cyclopenta[a]phenanthren-3-imine
• CAS: 32221-26-4
• 化学式: C₃₂H₆₀N₂O₅Si₃
• 分子量: 637.095
• InChiKey: PRZGIUIKCGRVGY-NWZOWSRLSA-N

物化性质

• 保留指数：
  2980;3290

计算性质

• 辛醇/水分配系数(LogP)：
  8.23
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  70.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  氢化可的松 在 吡啶 作用下， 反应 2.0h， 生成 3,20-Bis-(O-methyloxim)-cortisol-trimethylsilyl-ether
  参考文献：
  名称：

  Mass Fragmentography of Cortisol and Cortisone: Preliminary Studies on the Development of a Reference Method

  摘要：

  皮质醇和皮质酮是人体血浆中发现的两种主要糖皮质激素。通常通过免疫测定法测量皮质醇以评估肾上腺功能，但这些程序必须经过适当的质量控制，最好使用同位素稀释质谱法（GC-MS）测量的分析物目标值。已经研究了这些类固醇的三种衍生物的色谱和质谱特性，以开发一种简单快速的GC-MS方法。三甲基硅醚- O -甲氧基肟衍生物灵敏度较差，syn和anti异构体分为两个峰。环状甲基硼酸酯- O -甲氧基肟衍生物灵敏度极高，但难以制备，偶尔会通过某种未知机制引起皮质醇的11-氧化。该衍生物的11-羟基未经衍生化也会引起色谱问题。然而，烯醇三甲基硅醚易于制备，灵敏度极高（比三甲基硅醚- O -甲氧基肟衍生物高10-17倍）。获得了直线校准曲线，并且该方法可以使用三氘代皮质醇作为内部标准，在人体血浆中清晰地测量皮质醇和皮质酮，具有高特异性和敏感性。

  DOI：

  10.1135/cccc20020001

文献信息

• Mass Fragmentography of Cortisol and Cortisone: Preliminary Studies on the Development of a Reference Method
  作者：Hugh L. J. Makin、David J. H. Trafford、Norman F. Taylor

  DOI：10.1135/cccc20020001

  日期：——

  Cortisol and cortisone are the two main glucocorticoids found in human plasma. Cortisol is commonly measured as a means of assessing adrenal function, usually by immunoassay, but such procedures must be subject to proper quality control which ideally uses analyte target values measured by isotope dilution mass fragmentography (GC-MS). Three derivatives of these steroids have been investigated for their chromatographic and mass spectral characteristics in order to develop a simple and rapid GC-MS method for this purpose. Trimethylsilyl ether-O-methyloxime derivatives gave poor sensitivity and thesyn- andanti-isomers were resolved into two peaks. Cyclic methylboronate-O-methyloxime derivatives gave excellent sensitivity but were difficult to prepare, occasionally giving rise, by some unknown mechanism, to 11-oxidation of cortisol. The underivatised 11-hydroxyl of this derivative of cortisol also gave rise to chromatographic problems. Enol-trimethylsilyl ethers however were easy to prepare and gave excellent sensitivity (10-17 times that achieved with the trimethylsilyl ether-O-methyloxime derivatives). Straight line calibration graphs were obtained and the method gave clean traces allowing high specificity and sensitive measurement of cortisol and cortisone in human plasma using tri-deuterated cortisol as an internal standard.

  皮质醇和皮质酮是人体血浆中发现的两种主要糖皮质激素。通常通过免疫测定法测量皮质醇以评估肾上腺功能，但这些程序必须经过适当的质量控制，最好使用同位素稀释质谱法（GC-MS）测量的分析物目标值。已经研究了这些类固醇的三种衍生物的色谱和质谱特性，以开发一种简单快速的GC-MS方法。三甲基硅醚- O -甲氧基肟衍生物灵敏度较差，syn和anti异构体分为两个峰。环状甲基硼酸酯- O -甲氧基肟衍生物灵敏度极高，但难以制备，偶尔会通过某种未知机制引起皮质醇的11-氧化。该衍生物的11-羟基未经衍生化也会引起色谱问题。然而，烯醇三甲基硅醚易于制备，灵敏度极高（比三甲基硅醚- O -甲氧基肟衍生物高10-17倍）。获得了直线校准曲线，并且该方法可以使用三氘代皮质醇作为内部标准，在人体血浆中清晰地测量皮质醇和皮质酮，具有高特异性和敏感性。