18,27-dithia-14,22-dimethyl-1,4,7,10-tetraoxa-[10.3.3](1,2,6)cyclophane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 18,27-dithia-14,22-dimethyl-1,4,7,10-tetraoxa-[10.3.3](1,2,6)cyclophane
• 英文别名: 16,24-Dimethyl-3,6,9,12-tetraoxa-20,27-dithiatetracyclo[12.11.3.02,22.013,18]octacosa-1,13,15,17,22,24-hexaene；16,24-dimethyl-3,6,9,12-tetraoxa-20,27-dithiatetracyclo[12.11.3.02,22.013,18]octacosa-1,13,15,17,22,24-hexaene
• 化学式: C₂₄H₃₀O₄S₂
• 分子量: 446.632
• InChiKey: ATIJRWYUONWMRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  30
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  87.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1,2-双(2-溴乙氧基)乙烷 在 sodium sulfide 、 三溴化磷 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 乙醇 、 丙酮 、 苯 为溶剂， 反应 120.0h， 生成 18,27-dithia-14,22-dimethyl-1,4,7,10-tetraoxa-[10.3.3](1,2,6)cyclophane
  参考文献：
  名称：

  Conformational behavior of dithia[n.3.3](1,3,5)cyclophanes and dithia[n.3.3](1,2,6)cyclophanes

  摘要：

  The conformational behavior of a series of crown-fused dithia[n.3.3](1,2,6)cyclophanes (126-CPs) and dithia[n.3.3](l,3,5)cyclophanes (135-CPs) was investigated by variable-temperature H-1 and C-13 NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. Single crystal X-ray structure analysis showed that two thia-bridges in 126-CPs adopted a pseudochair-pseudochair (cc) conformation and the cyclophane decks underwent a ring-tilting motion in the case of [10.3.3](1,2,6)cyclophane (1a). In contrast, the thia-bridges in 135-CPs took both cc and pseudoboat-pseudochair (bc) conformations, and the ring-tilting process was also found in [10.3.3](1,3,5)cyclophane (2a). Variable temperature H-1 NMR study revealed that there was no wobbling-motion for two thia-bridges in 126-CPs while thia-bridges in 135-CPs experienced a wobbling-process with a conformational barrier of 9.21 and 8.80 kcal mol(-1), respectively, for 2a and [13.3.3](1,3,5)cyclophane (2b). DFT calculations for the two cyclophanes series revealed that 126-CPs preferred a cc conformation which was consistent with the experimental observation; similarly, 135-CPs took a preferential cc conformation, agreeing with 2a having a predominant cc conformer (cc:bc ratio=70:30), but not 2b having a predominant bc conformer (cc:bc ratio= 15:85) in the solid state. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.027

文献信息

• Conformational behavior of dithia[n.3.3](1,3,5)cyclophanes and dithia[n.3.3](1,2,6)cyclophanes
  作者：Jian-Wei Xu、Ting-Ting Lin、Yee-Hing Lai

  DOI：10.1016/j.tet.2005.01.027

  日期：2005.2

  The conformational behavior of a series of crown-fused dithia[n.3.3](1,2,6)cyclophanes (126-CPs) and dithia[n.3.3](l,3,5)cyclophanes (135-CPs) was investigated by variable-temperature H-1 and C-13 NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. Single crystal X-ray structure analysis showed that two thia-bridges in 126-CPs adopted a pseudochair-pseudochair (cc) conformation and the cyclophane decks underwent a ring-tilting motion in the case of [10.3.3](1,2,6)cyclophane (1a). In contrast, the thia-bridges in 135-CPs took both cc and pseudoboat-pseudochair (bc) conformations, and the ring-tilting process was also found in [10.3.3](1,3,5)cyclophane (2a). Variable temperature H-1 NMR study revealed that there was no wobbling-motion for two thia-bridges in 126-CPs while thia-bridges in 135-CPs experienced a wobbling-process with a conformational barrier of 9.21 and 8.80 kcal mol(-1), respectively, for 2a and [13.3.3](1,3,5)cyclophane (2b). DFT calculations for the two cyclophanes series revealed that 126-CPs preferred a cc conformation which was consistent with the experimental observation; similarly, 135-CPs took a preferential cc conformation, agreeing with 2a having a predominant cc conformer (cc:bc ratio=70:30), but not 2b having a predominant bc conformer (cc:bc ratio= 15:85) in the solid state. (C) 2005 Elsevier Ltd. All rights reserved.