3-ethylenedioxy-5,10-epoxy-18a-homo-estr-9(11)-ene-17-one | 646037-53-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 3-ethylenedioxy-5,10-epoxy-18a-homo-estr-9(11)-ene-17-one
• CAS: 646037-53-8
• 化学式: C₂₁H₂₈O₄
• 分子量: 344.451
• InChiKey: YVVGPDYVSUTKMF-IKLKHEEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  25.0
• 可旋转键数：
  1.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  48.06
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  3-ethylenedioxy-5,10-epoxy-18a-homo-estr-9(11)-ene-17-one 在 正丁基锂 、 1,1-二溴乙烷 、 magnesium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.5h， 生成 11-(4'-dimethylaminophenyl)-17β-hydroxy-17-(3-hydroxy-1-propynyl)-18a-homo-estra-5(10),9(11)-diene-3-one
  参考文献：
  名称：

  Hydrolytic behavior of 5α-hydroxy-11β- and 5β-hydroxy-11α-substituted 19-norsteroids

  摘要：

  Teutsch G. and Belanger A. treated 5alpha,10alpha epoxides with Grignard-reagents catalyzed by copper(l) ions. The reaction with steroidal epoxides proceeded with complete regio- and stereospecificity, leading exclusively to the 11beta-substituted compounds. According to our synthetic strategy, the 5, 10 epoxide isomers were not separated; instead, the pure 11beta, and in some cases, 11alpha-substituted molecules were isolated after the conjugate addition of the Grignard-reagents, followed by deketalization and dehydration. Surprisingly, appearance of a third compound was generally observed beside the expected deprotected products, and this compound turned out to have a 3-keto-5(10),9(11) structural unit. Starting from pure 3-ethylenedioxy-5alpha,10alpha-epoxy-estr-9(11)-ene-17-one and 3-ethylenedioxy-5beta,10beta-epoxy-estr-9(11)-ene-17-one, four model compounds were synthesized (11alpha- and 11beta-{4-[1,1-(ethylenedioxy)-ethyl]phenyl}-estra-, as well as 11alpha- and 11beta-cyclohexyl-estra-derivatives) to study the process of deprotection and dehydration. 3-keto-5(10),9(11)-derivatives were found to form after deketalization and dehydration only from 11alpha-substituted derivatives, while 11beta-derivatives resulted in only the expected 3-keto-5,9-diene structure. After observing this remarkable difference between the behavior of 11alpha-, 11beta-substituted isomers we decided to take a closer look at the processes of deketalization and dehydration. In order to carry out the hydrolysis under mild conditions, pyridinium paratoluenesulfonate, a weakly acidic salt, was applied. All the intermediate products observed by TLC were isolated. The outcome of the deprotection and elimination reactions can be rationalized by two factors: conjugation of olefins (with the 3-oxo-group or the 11-phenyl group) and orientation of groups to be eliminated. (C) 2003 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2003.07.003
• 作为产物：
  描述：

  3-ethylenedioxy-13β-ethyl-gona-5(10),9(11)-diene-17-one 在 六氯丙酮 、 双氧水 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 3.0h， 以89%的产率得到3-ethylenedioxy-5,10-epoxy-18a-homo-estr-9(11)-ene-17-one
  参考文献：
  名称：

  Hydrolytic behavior of 5α-hydroxy-11β- and 5β-hydroxy-11α-substituted 19-norsteroids

  摘要：

  Teutsch G. and Belanger A. treated 5alpha,10alpha epoxides with Grignard-reagents catalyzed by copper(l) ions. The reaction with steroidal epoxides proceeded with complete regio- and stereospecificity, leading exclusively to the 11beta-substituted compounds. According to our synthetic strategy, the 5, 10 epoxide isomers were not separated; instead, the pure 11beta, and in some cases, 11alpha-substituted molecules were isolated after the conjugate addition of the Grignard-reagents, followed by deketalization and dehydration. Surprisingly, appearance of a third compound was generally observed beside the expected deprotected products, and this compound turned out to have a 3-keto-5(10),9(11) structural unit. Starting from pure 3-ethylenedioxy-5alpha,10alpha-epoxy-estr-9(11)-ene-17-one and 3-ethylenedioxy-5beta,10beta-epoxy-estr-9(11)-ene-17-one, four model compounds were synthesized (11alpha- and 11beta-{4-[1,1-(ethylenedioxy)-ethyl]phenyl}-estra-, as well as 11alpha- and 11beta-cyclohexyl-estra-derivatives) to study the process of deprotection and dehydration. 3-keto-5(10),9(11)-derivatives were found to form after deketalization and dehydration only from 11alpha-substituted derivatives, while 11beta-derivatives resulted in only the expected 3-keto-5,9-diene structure. After observing this remarkable difference between the behavior of 11alpha-, 11beta-substituted isomers we decided to take a closer look at the processes of deketalization and dehydration. In order to carry out the hydrolysis under mild conditions, pyridinium paratoluenesulfonate, a weakly acidic salt, was applied. All the intermediate products observed by TLC were isolated. The outcome of the deprotection and elimination reactions can be rationalized by two factors: conjugation of olefins (with the 3-oxo-group or the 11-phenyl group) and orientation of groups to be eliminated. (C) 2003 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2003.07.003