8,11,14,17,20,23-hexaoxacyclotetracos-1-ene-3,5-diyne | 185378-92-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 8,11,14,17,20,23-hexaoxacyclotetracos-1-ene-3,5-diyne
• 英文别名: 1,4,7,10,13,16-Hexaoxacyclotetracos-18-ene-20,22-diyne；1,4,7,10,13,16-hexaoxacyclotetracos-18-en-20,22-diyne
• CAS: 185378-92-1
• 化学式: C₁₈H₂₆O₆
• 分子量: 338.401
• InChiKey: QLBXHCMJYPOOSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-Bromo-4-[2-[2-[2-[2-[2-(4-bromobut-2-ynoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]but-2-yne 在 四甲基乙二胺 、 potassium bromide 作用下， 以 四氢呋喃 为溶剂， 生成 (Z)-8,11,14,17,20,23-hexaoxacyclotetracos-3-ene-1,5-diyne 、 8,11,14,17,20,23-hexaoxacyclotetracos-1-ene-3,5-diyne
  参考文献：
  名称：

  Synthesis and Metal Ion Binding Studies of Enediyne-Containing Crown Ethers

  摘要：

  The 3-ene-1,5-diyne crown ether 5 is a novel enediyne-containing crown ether that was designed as a model system for a class of enediynes that might undergo alkali metal ion-triggered Bergman cyclization. We report the preparation of 5 by two different routes. In the shorter and preferable route, a carbenoid coupling reaction is employed to simultaneously construct the enediyne moiety and effect a macrocyclization of an acyclic bis(propargyl)bromide 15 to the 24-membered crown ether 5. Under standard reaction conditions, this carbenoid coupling produces as the major product the isomeric 5-ene-1,3-diyne-crown ethers (Z)-16 and (E)-16. The formation of 5-ene-1,3-diynes from the carbenoid coupling of propargyl bromides is unprecedented. We present evidence that it is the polyether nature of dibromide 15 that leads to the formation of the 5-ene-1,3-diyne-crown ether products. Judicious control of the reaction conditions can be used to produce either 5 or (Z)-16 from 15 in synthetically useful yields. Both enediyne-crown ethers 5 and (Z)-16 bind alkali metal ions, as evidenced by their ability to extract alkali metal picrates into organic solvents. Enediyne-crown ether 5 undergoes Bergman cyclization at 135 degrees C in DMSO/1,4-cyclohexadiene to produce the known o-xylyl crown ether 4. Crown ether 5 represents an enediyne in which molecular recognition of alkali metals might serve as a trigger for Bergman cyclization.

  DOI：

  10.1021/jo961583r

文献信息

• Synthesis and Metal Ion Binding Studies of Enediyne-Containing Crown Ethers
  作者：Mark M. McPhee、Sean M. Kerwin

  DOI：10.1021/jo961583r

  日期：1996.1.1

  The 3-ene-1,5-diyne crown ether 5 is a novel enediyne-containing crown ether that was designed as a model system for a class of enediynes that might undergo alkali metal ion-triggered Bergman cyclization. We report the preparation of 5 by two different routes. In the shorter and preferable route, a carbenoid coupling reaction is employed to simultaneously construct the enediyne moiety and effect a macrocyclization of an acyclic bis(propargyl)bromide 15 to the 24-membered crown ether 5. Under standard reaction conditions, this carbenoid coupling produces as the major product the isomeric 5-ene-1,3-diyne-crown ethers (Z)-16 and (E)-16. The formation of 5-ene-1,3-diynes from the carbenoid coupling of propargyl bromides is unprecedented. We present evidence that it is the polyether nature of dibromide 15 that leads to the formation of the 5-ene-1,3-diyne-crown ether products. Judicious control of the reaction conditions can be used to produce either 5 or (Z)-16 from 15 in synthetically useful yields. Both enediyne-crown ethers 5 and (Z)-16 bind alkali metal ions, as evidenced by their ability to extract alkali metal picrates into organic solvents. Enediyne-crown ether 5 undergoes Bergman cyclization at 135 degrees C in DMSO/1,4-cyclohexadiene to produce the known o-xylyl crown ether 4. Crown ether 5 represents an enediyne in which molecular recognition of alkali metals might serve as a trigger for Bergman cyclization.