17,20:20,21-二(亚甲二氧基)孕甾-4-烯-3-酮 | 6173-64-4

• 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
• 中文名称: 17,20:20,21-二(亚甲二氧基)孕甾-4-烯-3-酮
• 英文名称: cortexolone-BMD
• 英文别名: 17,20;20,21-bismethylenedioxypregn-4-en-3-one；17,20:20,21-bismethylenedioxy-4-pregnen-3-one；(20Ξ)-17,20;20,21-bis-methylenedioxy-pregn-4-en-3-one；(20Ξ)-17,20;20,21-Bis-methylendioxy-pregn-4-en-3-on
• CAS: 6173-64-4
• 化学式: C₂₃H₃₂O₅
• 分子量: 388.504
• InChiKey: WFZVFCIUAYURKP-KFEAHILISA-N

物化性质

• 溶解度：
  可溶于DCM、乙酸乙酯、甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  17,20:20,21-二(亚甲二氧基)孕甾-4-烯-3-酮 在 吡啶 、 sodium hydroxide 、 sodium borodeuteride 、 5% Pd-CaCO3 、 氢氟酸 、 氢气 、 三甲基铵三氧化硫共聚物 、 sodium hydroxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 吡啶 、 甲醇 、 乙醇 、 CH₃OD 、 重水 为溶剂， 反应 55.0h， 生成 [2,2,3β,4,4-d5]-3α,17α-dihydroxy-21-sulfooxy-5β-pregnan-20-one sodium
  参考文献：
  名称：

  Synthesis of 3- and 21-monosulfates of [2,2,3β,4,4-2H5]-tetrahydrocorticosteroids in the 5β-series as internal standards for mass spectrometry

  摘要：

  The 3- and 21-monosulfates of pentadeuterated 5 beta-tetrahydrocorticosteroides were synthesized, starting from cortisol and 11-deoxycotisol. The principal reactions used were (1) perdeuteration of the methylene groups adjacent to the 3-oxo group of 17,20:20,21-bismethylendioxy-5 beta-3-ketosteroids with NaOD in CH3OD followed by stereoselective reduction with NaBD4, (2) sulfation of hydroxy groups with sulfur trioxide-trimethylamine complex, and (3) removal of the 17,20:20,21-bismethylendioxy group with hydrogen fluoride. The labeled compounds can be used as internal standards in liquid chromatography/mass spectrometry assays for clinical and biochemical studies. (C) 2011 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2011.05.014
• 作为产物：
  描述：

  聚合甲醛 、 脱氧可的松 在 盐酸 作用下， 以 氯仿 、 水 为溶剂， 反应 5.0h， 以71%的产率得到17,20:20,21-二(亚甲二氧基)孕甾-4-烯-3-酮
  参考文献：
  名称：

  Synthesis of 3- and 21-monosulfates of [2,2,3β,4,4-2H5]-tetrahydrocorticosteroids in the 5β-series as internal standards for mass spectrometry

  摘要：

  The 3- and 21-monosulfates of pentadeuterated 5 beta-tetrahydrocorticosteroides were synthesized, starting from cortisol and 11-deoxycotisol. The principal reactions used were (1) perdeuteration of the methylene groups adjacent to the 3-oxo group of 17,20:20,21-bismethylendioxy-5 beta-3-ketosteroids with NaOD in CH3OD followed by stereoselective reduction with NaBD4, (2) sulfation of hydroxy groups with sulfur trioxide-trimethylamine complex, and (3) removal of the 17,20:20,21-bismethylendioxy group with hydrogen fluoride. The labeled compounds can be used as internal standards in liquid chromatography/mass spectrometry assays for clinical and biochemical studies. (C) 2011 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2011.05.014

文献信息

• Synthesis of multiply deuterated 3- and 21-monosulfates of allo-tetrahydrocorticosteroids as internal standards for mass spectrometry
  作者：Kuniko Mitamura、Takayuki Mabuchi、Kaori Nagae、Masataka Nakajima、Rina Matsumoto、Sachi Fujioka、Kanta Sato、Rika Satoh (née Okihara)、Takashi Iida、Shoujiro Ogawa、Alan F. Hofmann、Shigeo Ikegawa

  DOI：10.1016/j.steroids.2012.08.007

  日期：2012.11

  5alpha-11-ketosteroids with NaOD in CH(3)OD followed by reduction with NaBD(4), (2) epimerization of the 3beta-hydroxy group into a 3alpha configuration, (3) sulfation of hydroxy groups at C-3 or C-21 in the resulting substrates with sulfur trioxide-trimethylamine complex, and (4) removal of 17,20;20,21-bismethylenedioxy groups with hydrogen fluoride in ethanol. Isotopic purity was found to be satisfactory by MS

  对复杂生物基质中痕量成分的准确分析需要使用可靠的内标。对于液相色谱/质谱分析，分析物分子的同位素标记的稳定类似物是最合适的内标。在本文中，描述了用四个或五个氘原子标记的异四氢皮质类固醇的3-和21-单硫酸盐的合成。所使用的主要反应是（1）与5alpha-3-ketosteroids和/或5alpha-11-的17,20; 20,21-双亚甲基二氧基衍生物的3-和11-氧代基相邻的活性亚甲基的氢-氘交换反应。在CH（3）OD中具有NaOD的酮类固醇，然后与NaBD（4）还原，（2）将3beta-羟基差向异构化为3alpha构型，（3）用三氧化硫-三甲胺络合物将所得底物中的C-3或C-21处的羟基硫酸化，和（4）用乙醇中的氟化氢除去17,20; 20,21-双亚甲基二氧基。通过MS发现同位素纯度令人满意，并且将新化合物的NMR性质制成表格。标记的化合物可用作液相色谱/质谱分析中的内标，用于临床和生化研究。
• Bismethylenedioxy steroids and methods of making same
  申请人：MERCK &

  公开号：US02888457A1

  公开（公告）日：1959-05-26
• The photosensitized oxidation of α-keto enols: A singlet oxygen approach to 2-oxasteroids
  作者：Aryeh A. Frimer、Shlomo Ripstos、Vered Marks、Gladis Aljadeff、Judith Hameiri-Buch、Pessia Gilinsky-Sharon

  DOI：10.1016/s0040-4020(01)96177-0

  日期：1991.9

  Fluoride ion catalyzed photosensitized singlet oxygenation of 2-hydroxycyclohexa-2,5-dien-1-ones 15a and b and the related steroidal alpha-keto enols 18a-g, generated the cyclohexenone lactols 16a-b and the corresponding steroidal analogs 19a-g generally in moderate to good yields (60-75%). Since the lactols can be conveniently reduced to the desired 2-oxasteroids in high yields, this 1O2 route presents itself as a synthetically acceptable alternative to the previously reported BCA approach3a for the preparation of 2-oxasteroids, especially in the case of base sensitive compounds.