9-(t-butyldimethylsilyloxy)-4-oxa-1-nonyne | 197304-85-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 9-(t-butyldimethylsilyloxy)-4-oxa-1-nonyne
• 英文别名: Tert-butyldimethyl{[5-(prop-2-yn-1-yloxy)pentyl]oxy}silane；tert-butyl-dimethyl-(5-prop-2-ynoxypentoxy)silane
• CAS: 197304-85-1
• 化学式: C₁₄H₂₈O₂Si
• 分子量: 256.461
• InChiKey: VVEMTTCOMBSOGK-UHFFFAOYSA-N

物化性质

• 沸点：
  286.2±20.0 °C(Predicted)
• 密度：
  0.878±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.83
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  9-(t-butyldimethylsilyloxy)-4-oxa-1-nonyne 在 potassium tert-butylate 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 生成 5-Propa-1,2-dienyloxy-pentan-1-ol
  参考文献：
  名称：

  Intramolecular Reaction of (γ-Alkoxyallyl)stannane with Aldehyde:  Origin of the Stereoselectivities

  摘要：

  The intramolecular cyclization of simple acyclic (gamma-alkoxyallyl)stannane aldehydes 1, 2, and 12-15 was investigated to elucidate the relationship between the geometry of the double bond of the allylstannanes, the ring size of cyclic ethers produced by the cyclization, and the procedures for promoting the cyclization. The Lewis acid-mediated cyclization of 1-2, 12-13, and 14-15 gave the trans cyclic ethers 3, 39, and 41, respectively, either predominantly or exclusively irrespective of the geometry of the double bond and of the ring size of the cyclic ethers. The relationship in the thermal cyclization of 1 and 2, which gave the 6-membered cyclic ethers 4 and 3, was straightforward; the Z isomer 1 gave the cis product 4, and the E isomer 2 afforded the trans product 3. However, the relationship in the thermal cyclization of 12 and 13 which afforded the 5-membered cyclic ethers 39 and 40 was different from that expected from the cyclization via the well-accepted cyclic transition state, as observed in the case of 1 and 2. Both the Z (12) and E (13) isomers gave the cis cyclic ether 40 either predominantly or exclusively. The protic acid-mediated (or-catalyzed) cyclization of 12-13 and 14-15 gave the trans cyclic ethers 39 and 41, respectively, regardless of the geometry of the double bonds. On the other hand, the protic acid-promoted cyclization of 1 and 2 was very strange; the Z isomer 1 gave the cis isomer 4, and the E isomer 2 afforded the trans isomer 3. The mechanisms for these cyclization reactions are proposed.

  DOI：

  10.1021/jo971309c
• 作为产物：
  描述：

  1,5-戊二醇 、 alkaline earth salt of/the/ methylsulfuric acid 在 咪唑 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 9-(t-butyldimethylsilyloxy)-4-oxa-1-nonyne
  参考文献：
  名称：

  Intramolecular Reaction of (γ-Alkoxyallyl)stannane with Aldehyde:  Origin of the Stereoselectivities

  摘要：

  The intramolecular cyclization of simple acyclic (gamma-alkoxyallyl)stannane aldehydes 1, 2, and 12-15 was investigated to elucidate the relationship between the geometry of the double bond of the allylstannanes, the ring size of cyclic ethers produced by the cyclization, and the procedures for promoting the cyclization. The Lewis acid-mediated cyclization of 1-2, 12-13, and 14-15 gave the trans cyclic ethers 3, 39, and 41, respectively, either predominantly or exclusively irrespective of the geometry of the double bond and of the ring size of the cyclic ethers. The relationship in the thermal cyclization of 1 and 2, which gave the 6-membered cyclic ethers 4 and 3, was straightforward; the Z isomer 1 gave the cis product 4, and the E isomer 2 afforded the trans product 3. However, the relationship in the thermal cyclization of 12 and 13 which afforded the 5-membered cyclic ethers 39 and 40 was different from that expected from the cyclization via the well-accepted cyclic transition state, as observed in the case of 1 and 2. Both the Z (12) and E (13) isomers gave the cis cyclic ether 40 either predominantly or exclusively. The protic acid-mediated (or-catalyzed) cyclization of 12-13 and 14-15 gave the trans cyclic ethers 39 and 41, respectively, regardless of the geometry of the double bonds. On the other hand, the protic acid-promoted cyclization of 1 and 2 was very strange; the Z isomer 1 gave the cis isomer 4, and the E isomer 2 afforded the trans isomer 3. The mechanisms for these cyclization reactions are proposed.

  DOI：

  10.1021/jo971309c

文献信息

• Benzopyran or thiobenzopyran derivatives
  申请人：Chugai Seiyaku Kabushiki Kaisha

  公开号：US06645951B1

  公开（公告）日：2003-11-11

  The present invention provides novel benzopyran compounds, pharmaceutically acceptable salts thereof and stereoisomers thereof where the benzopyran compounds of the invention are compounds according to Formula I: The present invention further provides pharmaceutical compositions which possess anti-estrogenic activity and comprise at least one benzopyran compound of the invention and a method of treating breast cancer by administration of an effective amount of a benzopyran compound provided by the present invention.

  本发明提供了新颖的苯并吡喃化合物，其药学上可接受的盐及其立体异构体，其中本发明的苯并吡喃化合物是根据式I的化合物：本发明还提供了具有抗雌激素活性的药物组合物，包括本发明的至少一种苯并吡喃化合物，并通过给予本发明提供的苯并吡喃化合物的有效量来治疗乳腺癌的方法。