16α-hydroxy-5α-androstan-17-one | 25846-17-7

• 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: 16α-hydroxy-5α-androstan-17-one
• 英文别名: 16α-Hydroxy-5α-androstan-17-on；5alpha-Androstan-16alpha-ol-17-one；(5R,8R,9S,10S,13S,14S,16R)-16-hydroxy-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,15,16-tetradecahydrocyclopenta[a]phenanthren-17-one
• CAS: 25846-17-7
• 化学式: C₁₉H₃₀O₂
• 分子量: 290.446
• InChiKey: BHZXMBDTBMXJAX-ZLOBMTTQSA-N

物化性质

• 熔点：
  161-165 °C
• 沸点：
  413.1±28.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 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：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  16α-hydroxy-5α-androstan-17-one 在 sodium tetrahydroborate 、 silver(l) oxide 作用下， 以 甲醇 为溶剂， 反应 11.0h， 生成 16α-methoxy-5α-androstan-17α-ol
  参考文献：
  名称：

  Gas chromatography–mass spectrometric analysis of oxidative reactions of [19,19-2H2]19-hydroxy-3-deoxy androgens by placental aromatase

  摘要：

  Aromatase is a cytochrome P-450 enzyme complex that catalyzes the conversion of androst-4-ene-3,17-dione (AD) to estrone through three sequential oxidations of the 19-methyl group. 3-DeoxyAD (1) and its 5-ene isomer 4 are potent and good competitive aromatase inhibitors, which are converted by aromatase to the aldehyde derivatives 3 and 6, respectively, through 19-hydroxy intermediates 2 and 5, respectively. To study the deuterium isotope effect on the conversions of 19-ols 2 and 5 into the corresponding 19-als 3 and 6, we initially synthesized [19,19-H-2(2)]19-ols 2 and 5 starting from the corresponding non-labeled 19-als 3 and 6 through (NaBH4)-H-2 reduction of the 19-aldehyde group, followed by oxidation with pyridinium dichromate, and a subsequent NaB2H4 reduction. Approximately 1:1 mixtures of non-labeled (d(0)) and deuterated (d(2)) 19-ols 2 and 5 were separately incubated with human placental microsomes in the presence of NADPH under an air atmosphere, and deuterium contents of the recovered substrates and the 19-aldehyde products were determined by gas chromatography-mass spectrometry. In each experiment, the ratio of d(0) to d(2) of the recovered substrate along with that of do to all of the product were identical to the d(0) to d(2) ratio of the employed substrate irrespective of the incubation time, indicating that the 19-oxygenations of the 3-deoxy steroids 2 and 5 proceeded without a detectable isotope effect, as seen in the aromatization sequence of the natural substrate AD. (c) 2005 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2005.04.009
• 作为产物：
  描述：

  16α-bromo-5α-androstan-17-one 在 sodium hydroxide 作用下， 以 吡啶 、 水 为溶剂， 反应 0.33h， 以18%的产率得到16α-hydroxy-5α-androstan-17-one
  参考文献：
  名称：

  16α-halo-17-keto 类固醇的立体选择性水解和对 16α-bromo-17-ketones 和 2α-bromo-3-ketones 水解的长程取代效应

  摘要：

  摘要 16α-氯- ( 1a )、溴- ( 1b ) 和碘-3β-羟基-5-雄烯- 17-one ( 1c ) 的差向异构化通过在吡啶水溶液中用 0.2 当量 NaOH 短暂处理达到 16α-和 16β-卤代酮。平衡时的 16α-/16β-Halo 酮比对于 Cl 为 1.5，对于 Br 为 1.25，对于 I 为 1.0。动力学分析表明化合物 1a-c 通过 SN2 机制立体选择性地转化为相应的 16α-羟基衍生物 3，其中表观反应性的顺序是 Br > I > Cl。进行了许多 16α-溴-17-酮和 2α-溴-3-酮的水解。发现相应醇的产率取决于类固醇的远程结构特征。

  DOI：

  10.1016/0039-128x(85)90005-4

文献信息

• Deoxygenation of Steroidal Ring-D 16,17-Ketols with Timethylsilyl Iodide.
  作者：Masao NAGAOKA、Etsuko NAGASAWA、Mitsuteru NUMAZAWA

  DOI：10.1248/cpb.46.1857

  日期：——

  Reaction of various steroidal 16, 17-ketols, 16α-hydroxy-17-ketones 1-3, and 15, 16β-hydroxy-17-ketone 4, and 17β-hydroxy-16-ketones 5-7, and 17, along with methyl ethers of 16α- and 17β-ketols, 1 and 5, with an excess of trimethylsilyl iodide (TMSI) or with HI in CHCl3, produced the deoxygenated products, a mixture of the corresponding 17-and 16-ketones, in low to quantitative yields, in which the 17-ketone was the major product in each case. When the 16β-deuterated 16α-ketol 3 and the 17α-deuterated 17β-ketol 7 were reached with TMSI for a brief period (15 min), the deuterium content at C-16β and C-17α of the recovered steroids 3 and 7 was reduced by 17 and 35%, respectively. The present results indicate that the deoxygenation proceeds not only through a direct iodination pathway producing α-iodoketone but also through other reaction pathways.

  各种类固醇16,17-酮醇、16α-羟基-17-酮1-3、15,16-羟基-17-酮4，以及17β-羟基-16-酮5-7和17的反应，以及16α-和17β-酮醇的甲醚1和5与过量的三甲基硅基碘(TMSI)或HI在氯仿中的反应，产生脱氧产物，即相应的17-和16-酮的混合物，产量从低到定量不等，其中17-酮是每种情况下的主要产物。当16β-氘化的16α-酮醇3和17α-氘化的17β-酮醇7与TMSI短暂接触（15分钟），恢复的类固醇3和7中的C-16β和C-17α位的氘含量分别减少了17%和35%。当前结果表明，脱氧过程不仅通过直接碘化途径生成α-碘酮，还通过其他反应途径。
• Formation of 17.BETA.-Alkoxy-16-keto Steroids by Reaction of 16.ALPHA.-Hydroxy-17-keto and 17.BETA.-Hydroxy-16-keto Steroids with Trimethylsilyl Iodide in the Presence of Alkyl Alcohols.
  作者：Masao NAGAOKA、Michiko ENDO、Mitsuteru NUMAZAWA

  DOI：10.1248/cpb.48.1215

  日期：——

  steroids, 1, 3, and 8, and their 17beta-hydroxy-16-keto isomers, 4, 5, and 9, were transformed into the corresponding 17beta-alkoxy-16-keto derivatives on treatment with trimethylsilyl iodide (TMSI) in the presence of alkyl alcohol in CHCl3 in poor to high yields.

  将16α-羟基-17-酮类固醇1、3和8及其17β-羟基-16-酮类异构体4、5和9转化为相应的17β-烷氧基-16-酮衍生物在烷基醇存在下的CHCl3中，三甲基碘化碘（TMSI）的收率不高。
• Mechanistic Studies of Deoxygenation of Steroidal Ring-D 16,17-Ketols with Trimethylsilyl Iodide.
  作者：Masao NAGAOKA、Etsuko NAGASAWA、Sadao SATO、Mitsuteru NUMAZAWA

  DOI：10.1248/cpb.47.548

  日期：——

  Deoxygenation reaction of steroidal 16, 17-ketols 1, 2 and 6 as well as their silyl ethers 3 and 7 and 16- and 17-iodoketone analogs 11, 12, and 14 with trimethylsilyl iodide (TMSI) or HI under various conditions was examined. The results indicate that the deoxygenation producing 16- and 17-ketones 9 and 8 proceeds through multiple reaction pathways; a direct iodination of a siloxy group of the ketol silyl ethers by iodide ion to give the iodoketones (path b), addition of TMSI to a carbonyl group of the ketol silyl ethers to yield diiodo derivatives 22 and 23 through iodo-bis-TMS compounds 20 and 21 (path a), and cleavage of ether bond of dimers 15-18 initially produced are, at least, involved. In these sequences, rearrangement of the 16-ketols 1 and 2 to the 17β-ketol 6 also plays a significant role. The yields of the ketones 9 and 8 and their relative amounts would be dependent on the relative importance of each pathway in the reaction.

  研究了甾族16、17-酮醇1、2和6及其甲硅烷基醚3和7以及16-和17-碘酮类似物11、12和14与三甲基碘硅烷(TMSI)或HI在各种条件下的脱氧反应。结果表明，脱氧生成16-和17-酮9和8是通过多种反应途径进行的；通过碘离子直接碘化酮醇甲硅烷基醚的甲硅烷氧基，得到碘酮（路径b），将TMSI加成到酮醇甲硅烷基醚的羰基上，通过碘-双-TMS化合物生成二碘代衍生物22和23 20和21(路径a)，并且至少涉及最初产生的二聚体15-18的醚键的断裂。在这些序列中，16-酮醇 1 和 2 重排为 17β-酮醇 6 也发挥着重要作用。酮9和8的产率及其相对量将取决于反应中每个途径的相对重要性。
• Compounds useful for treating hypertriglyceridemia
  申请人：——

  公开号：US20040019026A1

  公开（公告）日：2004-01-29

  The present invention is directed to a method for treating a patient having hypertriglyceridemia comprising administering thereto a compound of the formula: 1

  本发明涉及一种治疗高甘油三酯血症患者的方法，包括向其投药式为1的化合物。
• Photoinduced molecular transformations. 104. Pathways of the photorearrangements of five-membered cyclic steroidal .alpha.-nitro ketones to N-hydroxy cyclic imides, cyclic hydroxamic acid, and cyclic imide
  作者：Hiroshi Suginome、Yoshitaka Kurokawa

  DOI：10.1021/jo00286a029

  日期：1989.12