4-[2-[2-[2-[2-[2-(4-Hydroxybut-2-ynoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]but-2-yn-1-ol | 185378-84-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-[2-[2-[2-[2-[2-(4-Hydroxybut-2-ynoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]but-2-yn-1-ol
• CAS: 185378-84-1
• 化学式: C₁₈H₃₀O₈
• 分子量: 374.431
• InChiKey: GKLHHRZAHIDJMR-UHFFFAOYSA-N

物化性质

• 沸点：
  509.8±45.0 °C(Predicted)
• 密度：
  1.150±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.9
• 重原子数：
  26
• 可旋转键数：
  17
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  95.8
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-[2-[2-[2-[2-[2-(4-Hydroxybut-2-ynoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]but-2-yn-1-ol 在 N,N-二甲基丙烯基脲 、 溴 、 三苯基膦 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 4.77h， 生成 (E)-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
• 作为产物：
  描述：

  羟丙基淀粉磷酸酯 在 正丁基锂 、 四甲基乙二胺 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 15.33h， 生成 4-[2-[2-[2-[2-[2-(4-Hydroxybut-2-ynoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]but-2-yn-1-ol
  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.