3β-fluoro-5αH-androstan-17-one | 361-80-8

• 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: 3β-fluoro-5αH-androstan-17-one
• 英文别名: 3β-fluoro-5α-androstan-17-one；3β-Fluor-5α-androstan-17-on；3β-Fluor-17-oxo-5α-androstan；(3S,5S,8R,9S,10S,13S,14S)-3-fluoro-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,15,16-tetradecahydrocyclopenta[a]phenanthren-17-one
• CAS: 361-80-8
• 化学式: C₁₉H₂₉FO
• 分子量: 292.437
• InChiKey: XSBKZRQOPNVGLF-LUJOEAJASA-N

物化性质

• 熔点：
  132-134 °C
• 沸点：
  379.5±42.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3β-fluoro-5αH-androstan-17-one 在 chromium(VI) oxide 作用下， 生成 3β-Fluor-5α-androstan-11,17-dion
  参考文献：
  名称：

  Jones,E.R.H. et al., Journal of the Chemical Society. Perkin transactions I, 1975, p. 2308 - 2312

  摘要：

  DOI：
• 作为产物：
  描述：

  3β-tosyloxyandrost-5-ene-17-one 在 乙醇 、 silver fluoride 、 钯 、 magnesium iodide 作用下， 生成 3β-fluoro-5αH-androstan-17-one
  参考文献：
  名称：

  Jacobsen; Jensen, Chemistry and industry, 1957, p. 172

  摘要：

  DOI：

文献信息

• [EN] C-HALOGEN BOND FORMATION<br/>[FR] FORMATION DE LIAISON C-HALOGÈNE
  申请人：GROVES JOHN T

  公开号：WO2013028639A1

  公开（公告）日：2013-02-28

  Methods of halogenating a carbon containing compound having an sp3 C-H bond are provided. Methods of fluorinating a carbon containing compound comprising halogenation with Cl or Br followed by nucleophilic substitution with F are provided. Methods of direct oxidative C-H fluorination of a carbon containing compound having an sp3 C-H bond are provided. The halogenated products of the methods are provided.

  提供了一种卤代含有sp3 C-H键的碳化合物的卤代方法。提供了一种包括用Cl或Br进行卤代，然后用F进行亲核取代的卤代碳化合物的氟化方法。提供了一种直接氧化C-H氟化的含有sp3 C-H键的碳化合物的方法。提供了这些方法的卤代产物。
• Fluorination of Secondary and Primary Alcohols by Thermal Decomposition of Electrochemically Generated Alkoxy Triphenylphosphonium Tetrafluoroborates.
  作者：Hatsuo MAEDA、Takashi KOIDE、Sayaka MATSUMOTO、Hidenobu OHMORI

  DOI：10.1248/cpb.44.1480

  日期：——

  Replacement of hydroxyl groups in secondary and primary alcohols (1) with a fluorine atom arising from tetrafluorobote anion has been performed by the electrochemical formation of alkoxy triphenylphosphonium tetrafluoroborarates (2) from 1, followed by their thermal decomposition. The procedure is quite simple, involving : (1) constant-current electrolysis of a mixture of 1, Ph3P, and Ph3PH·BF4 in CH2Cl2 in an undivided cell; (2) refluxing a tetrahydrofuran or dioxane solution of the residue afforded by evaporation of the solvent in vacuo after the electrolysis. Cyclic secondary alcohols such as 3β-hydroxy steroids and 2-adamantanol are transformed into the corresponding fluorides in satisfactory yields when the geometry of the leaving group in 2 is suitable for the substitution or an elimination process for 2 to give an alkene is stereochemically forbidden. The fluorination of steroidal alcohols and 4-phenyl-1-cyclohexanol proceeded with complete inversion, demonstrating that a fluorine atom from the tetrafluoroborate anion attacks from the side opposite to the phosphonium moiety in 2 via an SN2 mechanism rather than as SN1 mechanism. The fluorination of acyclic secondary and primary alcohols was performed by the present method in reasonable yields, although the reaction for the latter required more forcing conditions, such as refluxing in dioxane.

  次级和初级醇(1)中的羟基被四氟硼酸根衍生的氟原子取代，通过电化学形成烷氧基三苯基膦四氟硼酸盐(2)，然后进行热分解来实现。该过程相当简单，包括：(1)在无隔膜电池中对1、Ph3P和Ph3PH·BF4的CH2Cl2混合物进行恒电流电解；(2)将电解后在真空下蒸发溶剂得到的残渣的四氢呋喃或二氧六环溶液回流。当2中的离去基团的构型适合取代或消除过程，且2生成烯烃的立体化学被禁止时，环状次级醇如3β-羟基甾体和2-金刚烷醇可转化为相应的氟化物，产率令人满意。甾醇和4-苯基-1-环己醇的氟化反应进行完全反转，表明四氟硼酸根阴离子中的氟原子通过SN2机制从2中膦部分的对面攻击，而不是SN1机制。通过本方法，无环次级和初级醇的氟化反应在合理产率下进行，尽管后者的反应需要更强烈条件，如在二氧六环中回流。
• Convenient general preparation of oxygenated monofluoro- and gem-difluoro-5a-androstanes using diethylaminosulphur trifluoride
  作者：T. Geoffrey C. Bird、Peter M. Fredericks、Ewart R. H. Jones、G. Denis Meakins

  DOI：10.1039/c39790000065

  日期：——

  Hydroxy-ketones in the 5α-androstane series are converted into fluoro-ketones by diethylaminosulphur trifluoride under mild conditions; acetoxy-ketones give acetoxydifluorides under more vigorous conditions.

  在温和的条件下，三氟二乙氨基硫将5α-雄烷系列的羟基酮转化为氟酮。乙酰氧基酮在更剧烈的条件下生成乙酰氧基二氟化物。
• Potential organ or tumor-imaging agents. 16. Fluorinated androstanes and the prostate
  作者：Andre Castonguay、Raymond E. Counsell、R. W. Scot Skinner、Rodney V. Pozderac

  DOI：10.1021/jm00202a015

  日期：1978.4

  A series of substituted 5alpha-androstan-17beta-ols was synthesized and evaluated for their potential use in the development of a prostate imaging agent. The ability of the synthesized compounds to compete with [3H]-5alpha-dihydrotestosterone for rat prostate androgen receptor protein served as the screening assay. For 3-substituted derivatives, the order of binding to the androgen receptor protein

  合成了一系列取代的5α-雄激素-17β-醇，并评估了它们在前列腺成像剂开发中的潜在用途。合成的化合物与[3H]-5α-二氢睾酮竞争大鼠前列腺雄激素受体蛋白的能力用作筛选测定。对于3取代的衍生物，与雄激素受体蛋白的结合顺序为= O大于-OH大于H近似等于F。3beta-Fluoro-5alpha-androstan-17beta-ol被发现具有大约5％的去势大鼠丙酸睾丸激素的雄激素活性。3β-氟衍生物的低生物活性，再加上与引入氟18相关的合成障碍，导致我们寻找更合适的卤素类固醇作为潜在的放射诊断手段。
• Synthesis of Fluorinated Steroids Using a Novel Fluorinating Reagent Tetrabutylammonium Difluorodimethylphenylsilicate (TAMPS)
  作者：Pavel Herrmann、Jaroslav Kvíčala、Vladimír Pouzar、Hana Chodounská

  DOI：10.1135/cccc20081825

  日期：——

  Steroidal 3-fluoroderivatives were prepared from corresponding tosylates using tetrabutylammonium difluorodimethylphenylsilicate as fluorinating agent. The reaction was tested on all four possible C-3 and C-5 stereoisomers of cholestane and 17-oxoandrostane skeletons. In this reaction only one isomer was always formed with opposite configuration at C-3 to starting tosylate. The reaction is accompanied by elimination which affords a mixture of corresponding olefines.

  使用四丁基铵二氟二甲基苯基硅酸酯作为氟化试剂，从相应的tosylates制备了类固醇3-氟衍生物。该反应在胆甾烷和17-氧基雄甾烷骨架的所有四个可能的C-3和C-5立体异构体上进行了测试。在这个反应中，只形成了一个异构体，其C-3位置的构型与起始的tosylate相反。该反应伴随着消除作用，产生相应的烯烃混合物。