methyl 5-methyl-2-oxo-6-oxatricyclo<3.2.1.0^3,7>octane-4-carboxylate | 121901-06-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: methyl 5-methyl-2-oxo-6-oxatricyclo<3.2.1.0^3,7>octane-4-carboxylate
• 英文别名: methyl 5-methyl-2-oxo-6-oxatricyclo[3.2.1.0^3,7]octane-4-carboxylate
• CAS: 121901-06-2；131321-32-9
• 化学式: C₁₀H₁₂O₄
• 分子量: 196.203
• InChiKey: VVZUNOILCPITAW-QRZVSBQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.15
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  methyl 6a-methyl-4-oxa-3a,5,6,6a-tetrahydro-4H-cyclopentafuran-3a-carboxylate 以 苯 为溶剂， 反应 15.0h， 生成 methyl 5-methyl-2-oxo-6-oxatricyclo<3.2.1.0^3,7>octane-4-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