methyl 5-methyl-2-oxo-8-oxabicyclo<3.2.1>oct-6-ene-6-carboxylate | 114491-43-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: methyl 5-methyl-2-oxo-8-oxabicyclo<3.2.1>oct-6-ene-6-carboxylate
• 英文别名: 6-carbomethoxy-5-methyl-8-oxabicyclo<3.2.1>oct-6-en-2-one；8-oxabicyclo(3.2.1)oct-6-en-2-one；Methyl 5-methyl-2-oxo-8-oxabicyclo[3.2.1]oct-6-ene-6-carboxylate
• CAS: 114491-43-9
• 化学式: C₁₀H₁₂O₄
• 分子量: 196.203
• InChiKey: HZBNKPWBFGUDFF-UHFFFAOYSA-N

物化性质

• 沸点：
  299.0±40.0 °C(predicted)
• 密度：
  1.272±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 5-methyl-2-oxo-8-oxabicyclo<3.2.1>oct-6-ene-6-carboxylate 以 丙酮 为溶剂， 反应 2.0h， 以75%的产率得到methyl 6a-methyl-4-oxa-3a,5,6,6a-tetrahydro-4H-cyclopentafuran-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：

  乙酰丙酸 在 dirhodium tetraacetate 、 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 31.0h， 生成 methyl 5-methyl-2-oxo-8-oxabicyclo<3.2.1>oct-6-ene-6-carboxylate
  参考文献：
  名称：

  铑卡宾的串联环化-环加成反应。过程的范围和机械细节

  摘要：

  Reactions de diazo-1 pentanediones-2,5 avec des carboxyates de rhodium(II) qui Fourtnissent desylures cycliques reactifs

  DOI：

  10.1021/ja00164a034

文献信息

• Photochemical rearrangement of 8-oxabicyclo[3.2.1]oct-6-en-2-ones
  作者：Albert Padwa、Glen E. Fryxell、Lin Zhi、Susan F. Hornbuckle

  DOI：10.1016/s0040-4039(00)88467-1

  日期：1988.1
• PADWA, ALBERT;FRYXELL, GLEN E.;ZHI, LIN, J. AMER. CHEM. SOC., 112,(1990) N, C. 3100-3109
  作者：PADWA, ALBERT、FRYXELL, GLEN E.、ZHI, LIN

  DOI：——

  日期：——
• PADWA, ALBERT;FRYXELL, GLEN E.;ZHI, LIN;HORNBUCKLE, SUSAN F., TETRAHEDRON LETT., 29,(1988) N 52, C. 6889-6892
  作者：PADWA, ALBERT、FRYXELL, GLEN E.、ZHI, LIN、HORNBUCKLE, SUSAN F.

  DOI：——

  日期：——