trans-1,3-[C6H5-CH=CHC(O-C6H4-4-OMe)=CMe2] | 1174684-81-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: trans-1,3-[C6H5-CH=CHC(O-C6H4-4-OMe)=CMe2]
• 英文别名: 1-methoxy-4-[(1E)-4-methyl-1-phenylpenta-1,3-dien-3-yl]oxybenzene
• CAS: 1174684-81-1
• 化学式: C₁₉H₂₀O₂
• 分子量: 280.367
• InChiKey: DBDZUVRMVCGVJH-NTEUORMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  、 苯甲醛 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 6.5h， 以73%的产率得到trans-1,3-[C6H5-CH=CHC(O-C6H4-4-OMe)=CMe2]
  参考文献：
  名称：

  Reactivity of Allenylphosphonates toward Salicylaldehydes and Activated Phenols: Facile Synthesis of Chromenes and Substituted Butadienes

  摘要：

  The reaction of salicylaldehydes with allenylphosphonates in the presence of a base leads to a variety of phosphono-chromenes and allylic phosphonates. Optimization of reaction conditions reveals that DBU (base.) in DMSO (solvent) is the best combination in most cases, with DBU acting as an organocatalyst. PEG-400 also gave good results, but the yields were slightly lower than that in DMSO. Several of the key products have been characterized by single-crystal X-ray crystallography. Interconversion of E and Z isomers of phosphono-chromenes is demonstrated by P-31 NMR spectroscopy. A novel P-C bond cleavage reaction of some of these chromenes leading to substituted enones is also reported. In a few cases, phenol addition products are also isolated. In order to probe the pathways in the latter reaction, allenylphosphonates have also been treated with activated phenols in the presence of base to selectively afford either allylic phosphonyl ethers or vinylic phosphonyl ethers depending on the substituents on the allenylphosphonate. Theoretical calculations were consistent with experimental results. Finally, utilization of allylic phosphonyl ether in the Horner-Wadsworth-Emmons reaction to afford substituted trans-1,3-butadiene in good yields is demonstrated.

  DOI：

  10.1021/jo900896v

文献信息

• Reactivity of Allenylphosphonates toward Salicylaldehydes and Activated Phenols: Facile Synthesis of Chromenes and Substituted Butadienes
  作者：N. N. Bhuvan Kumar、M. Nagarjuna Reddy、K. C. Kumara Swamy

  DOI：10.1021/jo900896v

  日期：2009.8.7

  The reaction of salicylaldehydes with allenylphosphonates in the presence of a base leads to a variety of phosphono-chromenes and allylic phosphonates. Optimization of reaction conditions reveals that DBU (base.) in DMSO (solvent) is the best combination in most cases, with DBU acting as an organocatalyst. PEG-400 also gave good results, but the yields were slightly lower than that in DMSO. Several of the key products have been characterized by single-crystal X-ray crystallography. Interconversion of E and Z isomers of phosphono-chromenes is demonstrated by P-31 NMR spectroscopy. A novel P-C bond cleavage reaction of some of these chromenes leading to substituted enones is also reported. In a few cases, phenol addition products are also isolated. In order to probe the pathways in the latter reaction, allenylphosphonates have also been treated with activated phenols in the presence of base to selectively afford either allylic phosphonyl ethers or vinylic phosphonyl ethers depending on the substituents on the allenylphosphonate. Theoretical calculations were consistent with experimental results. Finally, utilization of allylic phosphonyl ether in the Horner-Wadsworth-Emmons reaction to afford substituted trans-1,3-butadiene in good yields is demonstrated.