4-methoxy-2-vinylbenzoic acid ethyl ester | 1401160-81-3

• 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: 4-methoxy-2-vinylbenzoic acid ethyl ester
• 英文别名: ethyl 4-methoxy-2-vinylbenzoate；Ethyl 2-ethenyl-4-methoxybenzoate
• CAS: 1401160-81-3
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: KPUFWLSVBORQAS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Umicore M31 、 4-methoxy-2-vinylbenzoic acid ethyl ester 以 二氯甲烷 为溶剂， 反应 8.0h， 以78%的产率得到cis-dichloro-(N,N′-bis[2,4,6-(trimethyl)phenyl]imidazolin-2-ylidene)(CHC₆H₃(OMe)CO₂Et)Ru
  参考文献：
  名称：

  Halide Exchange in Second-Generation cis-Dihalo Ruthenium Benzylidene Complexes

  摘要：

  The current article discusses the lability of the chloride ligands in cis-dichloro ruthenium benzylidene complexes featuring the NHC ligand N,N'-bis[2,4,6-(trimethyl)phenyl]imidazolin-2-ylidene] (SIMes) and an ester-chelating benzylidene ligand. A simple halide exchange reaction with iodide salts was used to assess the halide's lability in this type of complex. The starting compound bearing the cis-dichloro stereochemistry (cis-1) underwent rapid and selective exchange of the chloride trans to the SIMes ligand (cis-2). The substitution of the chloride cis to the NHC ligand for an iodide was found to be much slower, and the corresponding cis-diiodo compound could be isolated and characterized (cis-3). The latter compound undergoes fast and selective exchange of the iodide trans to the NHC ligand when an excess of a chloride source is added, and the fourth member of the family, bearing a chloride trans to the NHC ligand and a iodide cis to the NHC ligand (cis-4), was obtained. The four compounds have been fully characterized, and their catalytic activity was accessed using ring-opening metathesis polymerization of a norbornene derivative as the benchmark reaction. The activity of the initiators decreased within the series cis-4 > cis-1 > cis-2 > cis-3. The high activity of cis-4 could be traced back to the formation of the highest amounts of the corresponding trans-dihalo species, which are the actual active initiators.

  DOI：

  10.1021/om300785t
• 作为产物：
  描述：

  1-(2-溴-4-甲氧基苯基)-乙酮 在 四(三苯基膦)钯 、 氯化亚砜 、 sodium hypobromide 、 水 、 potassium carbonate 、 sodium hydroxide 作用下， 以 乙二醇二甲醚 、 水 为溶剂， 反应 28.0h， 生成 4-methoxy-2-vinylbenzoic acid ethyl ester
  参考文献：
  名称：

  Impact of Electronic Modification of the Chelating Benzylidene Ligand in cis-Dichloro-Configured Second-Generation Olefin Metathesis Catalysts on Their Activity

  摘要：

  A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP.

  DOI：

  10.1021/om500315t