25,26,27,28-Tetrapropoxy-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-4-carbaldehyde | 1165740-00-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 25,26,27,28-Tetrapropoxy-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-4-carbaldehyde
• CAS: 1165740-00-0；1204604-54-5
• 化学式: C₃₇H₄₀O₅S₄
• 分子量: 692.986
• InChiKey: HYVMUYLTGFADLD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.2
• 重原子数：
  46
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  155
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  25,26,27,28-Tetrapropoxy-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-4-carbaldehyde 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 3.0h， 以100%的产率得到(25,26,27,28-Tetrapropoxy-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaen-4-yl)methanol
  参考文献：
  名称：

  Uncommon Regioselectivity in the Thiacalix[4]arene Series: Gross Formylation of the Cone Conformer

  摘要：

  Thiacalix[4]arene immobilized in the cone conformation undergoes a direct Gross formylation reaction (Cl2CH-O-CH3/SnCl4/CH2Cl2) to give the upper-rim formylated thiacalixarene. Albeit using excess of the formylation agent and various reaction temperatures, only one formyl group is introduced into the meta position of the thiacalixarene skeleton. The surprising regioselectivity indicates dramatically different reactivity of the thiacalix[4]arene system when compared with a classical calix[4]arene analogue, which yields exclusively para isomers. The introduction of functional groups into the meta position represents an exceptional substitution pattern in thiacalixarene chemistry, which imparts in interesting conformational behavior to these compounds. The systematic NMR study revealed that the pinched cone-pinched cone equilibrium is remarkably shifted toward one pinched cone structure depending on the substitution.

  DOI：

  10.1021/jo902240h
• 作为产物：
  描述：

  25,26,27,28-tetrapropoxy-2,8,14,20-tetrathiacalix[4]arene 、 1,1-二氯-2-甲氧基乙烷 在 四氯化锡 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以71%的产率得到25,26,27,28-Tetrapropoxy-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-4-carbaldehyde
  参考文献：
  名称：

  硫杂杯[4]芳烃甲酰化反应中不常见的区域选择性

  摘要：

  为了揭示上边缘噻cali杂芳烃衍生化的替代方法，系统地研究了固定在1,3-交替构象中的相应四丙氧基硫杂杯[4]芳烃的甲酰化反应（Gros和/或Duff条件）。出人意料的是，尽管使用过量的甲酰化剂，但是仅两个甲酰基仅引入到噻菌杯芳烃骨架的间位。这些反应的意外区域选择性打开了噻咯烷芳烃化学中独特取代模式的大门。间位取代醛的形成是另一个例证，表明噻唑杯[4]芳烃体系的反应性与传统花萼[4]芳烃类似物的反应性显着不同。

  DOI：

  10.1021/jo9005574

文献信息

• Uncommon Regioselectivity in the Thiacalix[4]arene Series: Gross Formylation of the <i>Cone</i> Conformer
  作者：Ondrej Kundrat、Hana Dvorakova、Vaclav Eigner、Pavel Lhotak

  DOI：10.1021/jo902240h

  日期：2010.1.15

  Thiacalix[4]arene immobilized in the cone conformation undergoes a direct Gross formylation reaction (Cl2CH-O-CH3/SnCl4/CH2Cl2) to give the upper-rim formylated thiacalixarene. Albeit using excess of the formylation agent and various reaction temperatures, only one formyl group is introduced into the meta position of the thiacalixarene skeleton. The surprising regioselectivity indicates dramatically different reactivity of the thiacalix[4]arene system when compared with a classical calix[4]arene analogue, which yields exclusively para isomers. The introduction of functional groups into the meta position represents an exceptional substitution pattern in thiacalixarene chemistry, which imparts in interesting conformational behavior to these compounds. The systematic NMR study revealed that the pinched cone-pinched cone equilibrium is remarkably shifted toward one pinched cone structure depending on the substitution.
• Uncommon Regioselectivity in Thiacalix[4]arene Formylation
  作者：Ondrej Kundrat、Ivana Cisarova、Stanislav Böhm、Michaela Pojarova、Pavel Lhotak

  DOI：10.1021/jo9005574

  日期：2009.6.19

  the formylation reactions (Gross and/or Duff conditions) of the corresponding tetrapropoxythiacalix[4]arene immobilized in the 1,3-alternate conformation were systematically studied. Surprisingly, albeit using an excess of the formylation agent, only two formyl groups were introduced exclusively into the meta positions of thiacalixarene skeleton. Unexpected regioselectivity of these reactions opens

  为了揭示上边缘噻cali杂芳烃衍生化的替代方法，系统地研究了固定在1,3-交替构象中的相应四丙氧基硫杂杯[4]芳烃的甲酰化反应（Gros和/或Duff条件）。出人意料的是，尽管使用过量的甲酰化剂，但是仅两个甲酰基仅引入到噻菌杯芳烃骨架的间位。这些反应的意外区域选择性打开了噻咯烷芳烃化学中独特取代模式的大门。间位取代醛的形成是另一个例证，表明噻唑杯[4]芳烃体系的反应性与传统花萼[4]芳烃类似物的反应性显着不同。