14β-(cyanomethyl)-3-methoxyestra-1,3,5(10),15-tetraen-17-one | 930110-62-6

• 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: 14β-(cyanomethyl)-3-methoxyestra-1,3,5(10),15-tetraen-17-one
• 英文别名: 2-[(8R,9S,13S,14R)-3-methoxy-13-methyl-17-oxo-6,7,8,9,11,12-hexahydrocyclopenta[a]phenanthren-14-yl]acetonitrile
• CAS: 930110-62-6
• 化学式: C₂₁H₂₃NO₂
• 分子量: 321.419
• InChiKey: NSRDAVWULCBGNR-UKAVVXHISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  14β-(cyanomethyl)-3-methoxyestra-1,3,5(10),15-tetraen-17-one 在 氢氧化钾 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 8.0h， 以91%的产率得到1'-acetoxy-3-methoxy-2'-oxopyrrolidino[4',5':14β,15β]estra-1,3,5(10)-trien-17-one
  参考文献：
  名称：

  Synthesis and molecular structure of 14,15-pyrrolidino-and 14,16-ethano derivatives of estrone

  摘要：

  Hydrolysis of 3-methoxy-16 alpha-nitro-14,17-ethenoestra-1,3,5(10)-trien-17 beta-yl acetate under weakly basic conditions leads to formation of 3-methoxy-2'-oxopyrrolidino-[4',5':14 beta,15 beta]-estra-1,3,5 (10)-trien-17-one, the structure of which has been confirmed by X-ray analysis and some chemical transformations. The reactivity of 3-methoxy-16 alpha-nitro-14,17-ethanoestra-1,3,5(10)-trien-17 beta-yl acetate under various conditions of basic hydrolysis has been investigated. The derived compounds have been identified by means of NMR spectroscopy and X-ray analysis. (C) 2008 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2008.01.004
• 作为产物：
  描述：

  17-acetyloxy-3-methoxyestra-1,3,5(10),14,16-pentaene 在 碳酸氢钠 、 三苯基膦 作用下， 以 乙醇 、 水 、 苯 为溶剂， 反应 8.0h， 生成 14β-(cyanomethyl)-3-methoxyestra-1,3,5(10),15-tetraen-17-one
  参考文献：
  名称：

  3-Methoxy-16α-nitro-14,17-ethenoestra-1,3,5(10)-trien-17β-yl Acetate 和断裂介导的 14β,15β-FusedN-杂环和 14β-功能化烷基衍生物通路的合成

  摘要：

  3-甲氧基酯-1,3,5(10),14,16-戊烯-17-基乙酸酯 (1) 与硝基乙烯的狄尔斯-阿尔德反应生成 3-甲氧基-16-硝基-14,17-乙烯酯-1 ,3,5(10)-trien-17β-yl 乙酸酯 (2)。Cyclloadduct 2 可以用 TiCl3 还原，通过 σ 重排得到恶嗪 3，而用路易斯酸（TiCl4、SnCl4）处理 2 则生成环状羟肟酸 10 的衍生物；后者被视为分子内重排的产物。Cyclloadduct 2 受到弱碱诱导的 C(16)–C(17) 键断裂，释放出氧化腈中间体，该中间体可以被偶极试剂捕获或被三苯基膦还原。因此，用炔丙醇捕集氧化腈以50%的产率得到异恶唑12，用三苯基膦还原氧化腈以94%的产率得到腈9。

  DOI：

  10.1002/ejoc.200600629

文献信息

• Solvolysis of 14,17-etheno-bridged 16α-nitroestratrienyl acetate and lactam formation pathways studied by LC–NMR and LC–MS. Structures of minor products
  作者：Alexander V. Baranovsky、Dmitry A. Bolibrukh、Bernd Schneider

  DOI：10.1016/j.steroids.2015.08.009

  日期：2015.12

  The ethanol solvolysis of 3-methoxy-14,17-etheno-16 alpha-nitroestra-1,3,5(10)-trien-17 beta-yl acetate in the presence of NaHCO3 was studied by means of real-time NMR experiments, LC-SPE-NMR, and LC-MS. The pathway to form 3,methoxy-2'-oxopyrrolidino-[4',5':14 beta,15 beta]-estra-1,3,5(10)-trien-17-one was disclosed. The intermediacy of nitrile oxide and alkoxynitrone was postulated based on the analysis of the reaction products. The proposed mechanism of cleaving the bridge in the nitro compound is legal for the formation of N-acetoxylactams, nitriles, isoxazoles and isoxazolines. (C) 2015 Elsevier Inc. All rights reserved.
• Synthesis of 3-Methoxy-16α-nitro-14,17-ethenoestra-1,3,5(10)-trien-17β-yl Acetate and Fragmentation-Mediated Pathways to 14β,15β-FusedN-Heterocycles and 14β-Functionalised Alkyl Derivatives
  作者：Alexander V. Baranovsky、Dmitry A. Bolibrukh、James R. Bull

  DOI：10.1002/ejoc.200600629

  日期：2007.1

  The Diels–Alder reaction of 3-methoxyestra-1,3,5(10),14,16-pentaen-17-yl acetate (1) with nitroethylene gives 3-methoxy-16-nitro-14,17-ethenoestra-1,3,5(10)-trien-17β-yl acetate (2). Cycloadduct 2 can be reduced with TiCl3, giving oxazine 3 as a result of sigmatropic rearrangement, whereas the treatment of 2 with Lewis acids (TiCl4, SnCl4) leads to a derivative of the cyclic hydroximic acid 10; the

  3-甲氧基酯-1,3,5(10),14,16-戊烯-17-基乙酸酯 (1) 与硝基乙烯的狄尔斯-阿尔德反应生成 3-甲氧基-16-硝基-14,17-乙烯酯-1 ,3,5(10)-trien-17β-yl 乙酸酯 (2)。Cyclloadduct 2 可以用 TiCl3 还原，通过 σ 重排得到恶嗪 3，而用路易斯酸（TiCl4、SnCl4）处理 2 则生成环状羟肟酸 10 的衍生物；后者被视为分子内重排的产物。Cyclloadduct 2 受到弱碱诱导的 C(16)–C(17) 键断裂，释放出氧化腈中间体，该中间体可以被偶极试剂捕获或被三苯基膦还原。因此，用炔丙醇捕集氧化腈以50%的产率得到异恶唑12，用三苯基膦还原氧化腈以94%的产率得到腈9。
• Synthesis and molecular structure of 14,15-pyrrolidino-and 14,16-ethano derivatives of estrone
  作者：Alexander V. Baranovsky、Dmitry A. Bolibrukh、James R. Bull、Alexander S. Lyakhov、Vladimir A. Khripach

  DOI：10.1016/j.steroids.2008.01.004

  日期：2008.7

  Hydrolysis of 3-methoxy-16 alpha-nitro-14,17-ethenoestra-1,3,5(10)-trien-17 beta-yl acetate under weakly basic conditions leads to formation of 3-methoxy-2'-oxopyrrolidino-[4',5':14 beta,15 beta]-estra-1,3,5 (10)-trien-17-one, the structure of which has been confirmed by X-ray analysis and some chemical transformations. The reactivity of 3-methoxy-16 alpha-nitro-14,17-ethanoestra-1,3,5(10)-trien-17 beta-yl acetate under various conditions of basic hydrolysis has been investigated. The derived compounds have been identified by means of NMR spectroscopy and X-ray analysis. (C) 2008 Elsevier Inc. All rights reserved.