dimethyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6,7-dicarboxylate | 38462-94-1

• 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: dimethyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6,7-dicarboxylate
• 英文别名: Dimethyl 1-methoxy-8-oxo-12-oxatricyclo[7.2.1.02,7]dodeca-2,4,6,10-tetraene-10,11-dicarboxylate；dimethyl 1-methoxy-8-oxo-12-oxatricyclo[7.2.1.02,7]dodeca-2,4,6,10-tetraene-10,11-dicarboxylate
• CAS: 38462-94-1
• 化学式: C₁₆H₁₄O₇
• 分子量: 318.283
• InChiKey: CRGBBKZFDQNMTA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  dimethyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6,7-dicarboxylate 以 苯 为溶剂， 反应 8.0h， 以90%的产率得到dimethyl 2-(2-carbomethoxyphenyl)furan-3,4-dicarboxylate
  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：

  丁炔二酸二甲酯 、 o-methoxycarbonyl-α-diazoacetophenone 在 rhodium(II) acetate dimer 作用下， 以90%的产率得到dimethyl 8,9-dihydro-5-methoxy-9-oxa-5,8-epoxy-5H-benzocycloheptene-6,7-dicarboxylate
  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