2,2'-{[(E,E)-buta-1,3-dien-1,4-diyl]bis(furan-2,5-diyl)}bis[(E)-prop-2-enal] | 379257-93-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2,2'-{[(E,E)-buta-1,3-dien-1,4-diyl]bis(furan-2,5-diyl)}bis[(E)-prop-2-enal]
• 英文别名: (E)-3-[5-[(1E,3E)-4-[5-[(E)-3-oxoprop-1-enyl]furan-2-yl]buta-1,3-dienyl]furan-2-yl]prop-2-enal
• CAS: 379257-93-9
• 化学式: C₁₈H₁₄O₄
• 分子量: 294.307
• InChiKey: WBTBHOYRIXUHNC-VYUKIJHXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  triphenyl-[[5-[(1E,3E)-4-[5-(triphenylphosphaniumylmethyl)furan-2-yl]buta-1,3-dienyl]furan-2-yl]methyl]phosphanium 、 2,2'-{[(E,E)-buta-1,3-dien-1,4-diyl]bis(furan-2,5-diyl)}bis[(E)-prop-2-enal] 在 lithium 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 、
  参考文献：
  名称：

  Tetraepoxy[32]annulene(4.4.4.4) und `Tetraoxa[30]porphyrin(4.4.4.4)'-Dikationen

  摘要：

  Of the tetraepoxy[32]annulenes as well as the 'tetraoxa[30]porphyrin' dications, hithertoo only the (8.0.8.0) and the (6.2.6.2) systems are known to exist in several geometric isomers and to possess antiaromatic and aromatic character, respectively. Here we describe the still missing symmetric member of the [32]annulenes, the tetraepoxy[32]annulene(4.4.4.4) 1 and the corresponding 'tetraoxii[30]porphyrin(4.4.4.4)' dication 2. The cyclizing Wittig reaction of the dialdehyde 3 with the bis-phosphonium salt 7 at 70 yields the configurational isomers 1a (ZE,EE,EZ,EE), 1b (ZE,EE,EE,EE), and 1c (EZ,EE,EZ,EE). All isomers are antiaromatic; in la and 1c, the two (EE)-buta-1,3-diene-1,4-diyl bridges rotate around the adjacent sigma -bonds the rigidity of lb with 3 (EE) bridges prevents any dynamic character, Thc Wittig reaction of 3 with 7 at 20 only yields the kinetically controlled annulene le, and at 120, an excess of the thermodynamically most stable isomer la is formed. The structure of I is elucidated mainly by COSY and NOESY experiments, and the dynamic character of la and Ic is established by temperature-dependent H-1-NMR spectroscopy. The oxidation of the isomer mixture la-c with 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (DDQ) gives two isomeric 'tetraoxa[30]porphyrin(4.4.4.4)' dications 2 ' and 2 ", which are frozen conformers with the same (EZ,EE,EZ,EE)-configuration and geometrically related to 1c. Semiempirical calculations of I and 2 are in full agreement with the experimental results.

  DOI：

  10.1002/1522-2675(20010711)84:7<2022::aid-hlca2022>3.0.co;2-h
• 作为产物：
  描述：

  (1,3-二氧戊环-2-基)甲基三苯基溴化瞵 、 5,5'-[(E,E)-buta-1,3-dien-1,4-diyl]bis[furan-2-carbaldehyd] 在 lithium 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以62%的产率得到2,2'-{[(E,E)-buta-1,3-dien-1,4-diyl]bis(furan-2,5-diyl)}bis[(E)-prop-2-enal]
  参考文献：
  名称：

  Tetraepoxy[32]annulene(4.4.4.4) und `Tetraoxa[30]porphyrin(4.4.4.4)'-Dikationen

  摘要：

  Of the tetraepoxy[32]annulenes as well as the 'tetraoxa[30]porphyrin' dications, hithertoo only the (8.0.8.0) and the (6.2.6.2) systems are known to exist in several geometric isomers and to possess antiaromatic and aromatic character, respectively. Here we describe the still missing symmetric member of the [32]annulenes, the tetraepoxy[32]annulene(4.4.4.4) 1 and the corresponding 'tetraoxii[30]porphyrin(4.4.4.4)' dication 2. The cyclizing Wittig reaction of the dialdehyde 3 with the bis-phosphonium salt 7 at 70 yields the configurational isomers 1a (ZE,EE,EZ,EE), 1b (ZE,EE,EE,EE), and 1c (EZ,EE,EZ,EE). All isomers are antiaromatic; in la and 1c, the two (EE)-buta-1,3-diene-1,4-diyl bridges rotate around the adjacent sigma -bonds the rigidity of lb with 3 (EE) bridges prevents any dynamic character, Thc Wittig reaction of 3 with 7 at 20 only yields the kinetically controlled annulene le, and at 120, an excess of the thermodynamically most stable isomer la is formed. The structure of I is elucidated mainly by COSY and NOESY experiments, and the dynamic character of la and Ic is established by temperature-dependent H-1-NMR spectroscopy. The oxidation of the isomer mixture la-c with 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (DDQ) gives two isomeric 'tetraoxa[30]porphyrin(4.4.4.4)' dications 2 ' and 2 ", which are frozen conformers with the same (EZ,EE,EZ,EE)-configuration and geometrically related to 1c. Semiempirical calculations of I and 2 are in full agreement with the experimental results.

  DOI：

  10.1002/1522-2675(20010711)84:7<2022::aid-hlca2022>3.0.co;2-h

文献信息

• Tetraepoxy[32]annulene(4.4.4.4) und `Tetraoxa[30]porphyrin(4.4.4.4)'-Dikationen
  作者：Gottfried Märkl、Jürgen Stiegler、Peter Kreitmeier

  DOI：10.1002/1522-2675(20010711)84:7<2022::aid-hlca2022>3.0.co;2-h

  日期：2001.7.11

  Tetraepoxy[32]annulenes(4.4.4.4) and `Tetraoxa[30]porphyrin(4.4.4.4)' Dications Of the tetraepoxy[32]annulenes as well as the `tetraoxa[30]porphyrin' dications, hithertoo only the (8.0.8.0) and the (6.2.6.2) systems are known to exist in several geometric isomers and to possess antiaromatic and aromatic character, respectively. Here we describe the still missing symmetric member of the [32]annulenes