6,9,12,15,18,21-hexaoxa-1-thiacyclopentacosa-3,23-diyne | 185378-86-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,9,12,15,18,21-hexaoxa-1-thiacyclopentacosa-3,23-diyne
• 英文别名: 1,4,7,10,13,16-Hexaoxa-21-thiacyclopentacosa-18,23-diyne
• CAS: 185378-86-3
• 化学式: C₁₈H₂₈O₆S
• 分子量: 372.483
• InChiKey: MEXXSEJARGTVED-UHFFFAOYSA-N

物化性质

• 沸点：
  552.3±50.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  80.7
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  6,9,12,15,18,21-hexaoxa-1-thiacyclopentacosa-3,23-diyne 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.25h， 以75%的产率得到4,9,12,15,18,21-hexaoxa-1-thiacyclopentacosa-3,23-diyne 1-oxide
  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：

  4-[2-[2-[2-[2-[2-(4-Hydroxybut-2-ynoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]but-2-yn-1-ol 在 sodium sulfide 、 aluminum oxide 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 6,9,12,15,18,21-hexaoxa-1-thiacyclopentacosa-3,23-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, DNA cleavage, and cytotoxicity of a series of bis(propargylic) sulfone crown ethers
  作者：Mark M. McPhee、Sean M. Kerwin

  DOI：10.1016/s0968-0896(01)00150-x

  日期：2001.11

  molecular recognition of specific alkali metal ions with DNA damage may display selective cleavage of DNA under conditions of elevated alkali metal ion levels reported to exist in certain cancer cells. We have prepared a homologous series of compounds in which a DNA reactive moiety, a bis(propargylic) sulfone, is incorporated into an alkali metal ion binding crown ether ring. Using the alkali metal ion pricrate

  据报道，某些癌细胞中存在着碱金属离子水平升高的情况，将特定碱金属离子的分子识别与DNA损伤相结合的化合物可能会显示DNA的选择性裂解。我们制备了一系列同源化合物，其中将DNA反应性部分双（炔丙基）砜掺入与碱金属离子结合的冠醚环中。使用碱金属离子多价萃取法测定这些冠醚结合Li（+），Na（+）和K（+）离子的能力。对于一系列冠醚，Li（+）离子的缔合常数通常较低（<2 x 10（4）M（-1））。只有两个双（炔丙基）砜冠醚与Na（+）或K（+）离子缔合（K（a）4-8 x 10（4）M（-1）），而Na（+ ）或K（+）离子。确定了这些化合物在存在Li（+），Na（+）和K（+）离子的情况下在pH 7.4时切割超螺旋DNA的能力。与Na（+）和K（+）相比，在存在Na（+）或K（+）离子的情况下，结合Na（+）和K（+）的两个冠醚显示DNA裂解效率的适度提高。与非冠醚大环双（炔丙基）砜相比，
• 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.