11β,17,21-trihydroxy-pregn-4-ene-3,20-dione-bis-(O-methyl oxime ) | 3091-92-7

• 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: 11β,17,21-trihydroxy-pregn-4-ene-3,20-dione-bis-(O-methyl oxime )
• 英文别名: 11β,17,21-trihydroxy-pregn-4-ene-3,20-dione-bis-(O-methyl oxime )；11β,17,21-Trihydroxy-pregn-4-en-3,20-dion-bis-(O-methyl-oxim)
• CAS: 3091-92-7
• 化学式: C₂₃H₃₆N₂O₅
• 分子量: 420.549
• InChiKey: CVALRSPPBVXWSX-JZYPGELDSA-N

物化性质

• 熔点：
  205-208 °C
• 沸点：
  569.6±60.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.65
• 重原子数：
  30.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  103.87
• 氢给体数：
  3.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  11β,17,21-trihydroxy-pregn-4-ene-3,20-dione-bis-(O-methyl oxime ) 、 三甲基硅咪唑 反应 1.0h， 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
• 作为产物：
  描述：

  21-acetoxy-17-hydroxy-pregn-4-ene-3,11,20-trione-3,20-bis-(O-methyl oxime ) 在 sodium tetrahydroborate 作用下， 生成 11β,17,21-trihydroxy-pregn-4-ene-3,20-dione-bis-(O-methyl oxime )
  参考文献：
  名称：

  Brooks et al., Journal of the Chemical Society, 1958, p. 4614,4620

  摘要：

  DOI：

文献信息

• Diethylhydrogensilyl-cyclic diethylsilylene derivatives in gas chromatography/mass spectrometry of hydroxylated steroids. V. Analysis of cortisol and 6.BETA.-hydroxycortisol in human urine.
  作者：Masataka Ishibashi、Hideki Takayama、Yumiko Nakagawa、Noriaki Harima

  DOI：10.1248/cpb.36.845

  日期：——

  A gas chromatography/selected ion monitoring (GC/SIM) method for a simultaneous determination of cortisol (Kendall's compound 'F' : F) and its hydroxylated metabolite, 6β-hydroxycortisol (6OHF) in human urine has been developed using [2H3] cortisol as an internal standard. These compounds were analyzed as their methyloxime-diethylhydrogensilyl-cyclicdiethylsilylene derivatives. Gas chromatography of the F derivative showed a fairly broad single peak, whereas the 6OHF derivative exhibited a well-resolved doublet peak corresponding to the structral syn- and anti-isomers. The mass spectra were characterized by their intense molecular ion peaks and by their inherent ions of [M-OCH3]+, [M-diethyl-hydrogensilanol (DEHSOH)]+., and [M-OCH3-DEHSOH]+. When GC/SIM was carried out using their base peak ions at m/z 559 for F and 557 for 6OHF, the sensitivity for F was about 10 pg with signal-to-noise ratio of more than 10, and this was about a 5 times higher response factor than that of 6OHF. The calibration graphs were found to be linear in the observed range covering the concentrations found in healthy human urine.

  以[2H3]皮质醇为内标，开发了一种气相色谱/选择离子监测（GC/SIM）方法，用于同时测定人体尿液中的皮质醇（肯德尔化合物'F'：F）及其羟化代谢物 6β-hydroxycortisol (6OHF)。这些化合物以其甲基肟-二乙基氢根硅基-环二乙基硅基衍生物的形式进行分析。F 衍生物的气相色谱法显示出一个相当宽的单峰，而 6OHF 衍生物则显示出一个与结构同分异构体和反异构体相对应的分辨率很高的双峰。质谱的特征是其强烈的分子离子峰和固有离子[M-OCH3]+、[M-二乙基-氢硅醇（DEHSOH）]+和[M-OCH3-DEHSOH]+。利用 F 和 6OHF 的基峰离子 m/z 559 和 557 进行 GC/SIM 分析时，F 的灵敏度约为 10 pg，信噪比大于 10，响应系数约为 6OHF 的 5 倍。校准图在观测范围内呈线性，涵盖了健康人体尿液中的浓度。