methyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6-carboxylate | 74011-20-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: methyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6-carboxylate
• 英文别名: Methyl 1-methoxy-8-oxo-12-oxatricyclo[7.2.1.02,7]dodeca-2,4,6,10-tetraene-11-carboxylate；methyl 1-methoxy-8-oxo-12-oxatricyclo[7.2.1.02,7]dodeca-2,4,6,10-tetraene-11-carboxylate
• CAS: 74011-20-4
• 化学式: C₁₄H₁₂O₅
• 分子量: 260.246
• InChiKey: VPKZEHRZFZNERA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6-carboxylate 以 苯 为溶剂， 反应 4.0h， 以50%的产率得到methyl 3a,8b-dihydro-8b-methoxy-4-oxa-4H-indeno<1,2-b>furan-3a-carboxylate
  参考文献：
  名称：

  Studies dealing with the excited-state behavior of substituted 8-oxabicyclo[3.2.1]oct-6-en-2-ones

  摘要：

  A series of 8-oxabicyclo [3.2.1]oct-6-en-2-ones was prepared by the rhodium(II)-catalyzed cyclization-cycloaddition reaction of alpha-diazopentanedione with various alkynes. The photochemical behavior of these oxabicyclic enones was investigated. Both direct and sensitized photolysis cleanly results in a 1,3-acyl shift. A slower, secondary photoprocess involving intramolecular hydrogen atom transfer and intramolecular cycloaddition of the resulting ketene was also uncovered. The photobehavior of the closely related 9-oxabenzocycloheptene system was also examined. The initially formed 1,3-sigmatropic rearranged product was found to undergo a novel 1,4-methoxyl migration on extended photolysis. The photochemistry of the homologous 7-oxabicyclo[2.2.1]hepten-2-one was studied. The results obtained can be interpreted in terms of an initial Norrish type I cleavage. The resulting diradical either couples to give the 1,3-acyl shift product or undergoes bond fragmentation, giving products derived from a stepwise retro-Diels-Alder reaction.

  DOI：

  10.1021/jo00003a032
• 作为产物：
  描述：

  丙炔酸甲酯 、 o-methoxycarbonyl-α-diazoacetophenone 在 rhodium(II) acetate dimer 作用下， 以80%的产率得到methyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6-carboxylate
  参考文献：
  名称：

  Studies dealing with the excited-state behavior of substituted 8-oxabicyclo[3.2.1]oct-6-en-2-ones

  摘要：

  A series of 8-oxabicyclo [3.2.1]oct-6-en-2-ones was prepared by the rhodium(II)-catalyzed cyclization-cycloaddition reaction of alpha-diazopentanedione with various alkynes. The photochemical behavior of these oxabicyclic enones was investigated. Both direct and sensitized photolysis cleanly results in a 1,3-acyl shift. A slower, secondary photoprocess involving intramolecular hydrogen atom transfer and intramolecular cycloaddition of the resulting ketene was also uncovered. The photobehavior of the closely related 9-oxabenzocycloheptene system was also examined. The initially formed 1,3-sigmatropic rearranged product was found to undergo a novel 1,4-methoxyl migration on extended photolysis. The photochemistry of the homologous 7-oxabicyclo[2.2.1]hepten-2-one was studied. The results obtained can be interpreted in terms of an initial Norrish type I cleavage. The resulting diradical either couples to give the 1,3-acyl shift product or undergoes bond fragmentation, giving products derived from a stepwise retro-Diels-Alder reaction.

  DOI：

  10.1021/jo00003a032