9,18-(ethylenedioxy)-2,11-dithia<3.3>metacyclophane | 131079-20-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 9,18-(ethylenedioxy)-2,11-dithia<3.3>metacyclophane
• 英文别名: 15,18-dioxa-7,21-dithiatetracyclo[11.6.3.05,19.09,14]docosa-1(19),2,4,9,11,13-hexaene
• CAS: 131079-20-4
• 化学式: C₁₈H₁₈O₂S₂
• 分子量: 330.472
• InChiKey: QWUOLUUOKPSSOC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  69.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2,6-dimethylphenoxide 在 过氧化苯甲酰 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醇 、 苯 为溶剂， 反应 39.0h， 生成 9,18-(ethylenedioxy)-2,11-dithia<3.3>metacyclophane
  参考文献：
  名称：

  Synthesis and conformational study of 9,18-(ethylenedioxy)-2,11-dithia[3.3]metacyclophane: the propelling behavior of the three bridges in a [3.4.3](1,2,3)cyclophane

  摘要：

  A general approach which involved first the introduction of the central oxy or dioxy bridge and subsequent intramolecular coupling reactions to form the two thia bridges was employed in the syntheses of the 1,2,3-triply bridged cyclophanes 2, 3, and 4. The attempted routes to potential precursors of 2 were unsuccessful while the tetrabromide 16 could be synthesized. Intramolecular cyclizations of the latter, however, failed to yield 4, possibly due to unfavorable stereochemistry of the intermediate leading to the second intramolecular coupling reaction. The tetrabromide 18, with a central bridge of an appropriate length, successfully led to the formation of 3. The conformational behavior of 3 was analyzed by dynamic H-1 NMR spectroscopy. The ethylenedioxy bridge is believed to adopt the symmetrical ''boat'' conformation. All three bridges, however, undergo unrestricted pseudorotation, represented by free conformational interconversion 3b reversible 3c, at room temperature. A relatively frozen conformation 3b (3c) was observed at the low-temperature limit. Flipping processes of the ethylenedioxy bridge and the two thia bridges are found to be interdependent, resulting in an overall propelling process with a common conformational barrier estimated at ca. 45 kJ mol-1.

  DOI：

  10.1021/jo00001a050

文献信息

• LAI, YEE-HING;TAN, CHIN-WEE, J. ORG. CHEM., 56,(1991) N, C. 264-267
  作者：LAI, YEE-HING、TAN, CHIN-WEE

  DOI：——

  日期：——
• Synthesis and conformational study of 9,18-(ethylenedioxy)-2,11-dithia[3.3]metacyclophane: the propelling behavior of the three bridges in a [3.4.3](1,2,3)cyclophane
  作者：Yee Hing Lai、Chin Wee Tan

  DOI：10.1021/jo00001a050

  日期：1991.1

  A general approach which involved first the introduction of the central oxy or dioxy bridge and subsequent intramolecular coupling reactions to form the two thia bridges was employed in the syntheses of the 1,2,3-triply bridged cyclophanes 2, 3, and 4. The attempted routes to potential precursors of 2 were unsuccessful while the tetrabromide 16 could be synthesized. Intramolecular cyclizations of the latter, however, failed to yield 4, possibly due to unfavorable stereochemistry of the intermediate leading to the second intramolecular coupling reaction. The tetrabromide 18, with a central bridge of an appropriate length, successfully led to the formation of 3. The conformational behavior of 3 was analyzed by dynamic H-1 NMR spectroscopy. The ethylenedioxy bridge is believed to adopt the symmetrical ''boat'' conformation. All three bridges, however, undergo unrestricted pseudorotation, represented by free conformational interconversion 3b reversible 3c, at room temperature. A relatively frozen conformation 3b (3c) was observed at the low-temperature limit. Flipping processes of the ethylenedioxy bridge and the two thia bridges are found to be interdependent, resulting in an overall propelling process with a common conformational barrier estimated at ca. 45 kJ mol-1.