Methyl 4-(1,3-benzodithiol-2-ylidenemethyl)benzoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Methyl 4-(1,3-benzodithiol-2-ylidenemethyl)benzoate
• 化学式: C₁₆H₁₂O₂S₂
• 分子量: 300.402
• InChiKey: CWKOSECYMJZGMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 4-(1,3-benzodithiol-2-ylidenemethyl)benzoate 在 碘 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以28%的产率得到
  参考文献：
  名称：

  Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene over Ethane

  摘要：

  Here we report a soft porous crystal possessing hemilabile cross-links in its framework that exhibits exclusive gate opening for ethylene, enabling the discriminatory adsorption of ethylene over ethane. A Co-based porous coordination polymer (PCP) bearing vinylogous tetrathiafulvalene (VTTF) ligands, [Co(VTTF)], forms Co-S bonds as intermolecular cross-links in its framework in the evacuated closed state. The PCP recognizes ethylene via d-pi complexation on the accessible metal site that displaces and cleaves the Co-S bond to "unlock" the closed structure. This ethylene-triggered unlocking event facilitates remarkable nonporous-to-porous transformations that open up accessible void space. This structural transformation follows a two-step gate-opening process. Each phase, including the intermediate structure, was successfully characterized by single-crystal X-ray diffraction analysis, which revealed an intriguing "half-open" structure suggestive of a disproportionate gate-opening phenomenon. The gate-opening mechanism was also investigated theoretically; density functional theory and Monte Carlo calculations revealed that the unique "half-open" phase corresponds to a substantially stable intermediate over the possible transformation trajectories. While ethylene opens the gate, ethane does not . because it is unable to coordinate to the Co center. This feature is maintained even at pressures above 1 MPa and at a temperature of 303 K, demonstrating the potential of the "gate-locking/unlocking" mechanism that exploits the hemilabile cross-linking in soft porous crystals.

  DOI：

  10.1021/jacs.7b10110
• 作为产物：
  描述：

  1,3-benzodithiol-2-ylium tetrafluoroborate 在 正丁基锂 、 sodium iodide 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 16.67h， 生成 Methyl 4-(1,3-benzodithiol-2-ylidenemethyl)benzoate
  参考文献：
  名称：

  Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene over Ethane

  摘要：

  Here we report a soft porous crystal possessing hemilabile cross-links in its framework that exhibits exclusive gate opening for ethylene, enabling the discriminatory adsorption of ethylene over ethane. A Co-based porous coordination polymer (PCP) bearing vinylogous tetrathiafulvalene (VTTF) ligands, [Co(VTTF)], forms Co-S bonds as intermolecular cross-links in its framework in the evacuated closed state. The PCP recognizes ethylene via d-pi complexation on the accessible metal site that displaces and cleaves the Co-S bond to "unlock" the closed structure. This ethylene-triggered unlocking event facilitates remarkable nonporous-to-porous transformations that open up accessible void space. This structural transformation follows a two-step gate-opening process. Each phase, including the intermediate structure, was successfully characterized by single-crystal X-ray diffraction analysis, which revealed an intriguing "half-open" structure suggestive of a disproportionate gate-opening phenomenon. The gate-opening mechanism was also investigated theoretically; density functional theory and Monte Carlo calculations revealed that the unique "half-open" phase corresponds to a substantially stable intermediate over the possible transformation trajectories. While ethylene opens the gate, ethane does not . because it is unable to coordinate to the Co center. This feature is maintained even at pressures above 1 MPa and at a temperature of 303 K, demonstrating the potential of the "gate-locking/unlocking" mechanism that exploits the hemilabile cross-linking in soft porous crystals.

  DOI：

  10.1021/jacs.7b10110