ethyl 6-bromo-5-oxotricyclo<6.5.0.0^2,9>tridec-11-ene-4-carboxylate | 159145-55-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 6-bromo-5-oxotricyclo<6.5.0.0^2,9>tridec-11-ene-4-carboxylate
• 英文别名: Ethyl 6-bromo-5-oxotricyclo[6.5.0.0~2,9~]tridec-11-ene-4-carboxylate；ethyl 6-bromo-5-oxotricyclo[6.5.0.02,9]tridec-11-ene-4-carboxylate
• CAS: 159145-55-8
• 化学式: C₁₆H₂₁BrO₃
• 分子量: 341.245
• InChiKey: HOAXNDJNGKTXOR-UHFFFAOYSA-N

物化性质

• 沸点：
  411.5±45.0 °C(predicted)
• 密度：
  1.359±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 6-bromo-5-oxotricyclo<6.5.0.0^2,9>tridec-11-ene-4-carboxylate 在 盐酸 、 硫酸 、 溴 、 lithium carbonate 、 对甲苯磺酸 、 溶剂黄146 、 lithium bromide 、 锌 作用下， 以 乙醚 、 N,N-二甲基乙酰胺 、 乙二醇 、 丙酮 、 苯 为溶剂， 反应 53.34h， 生成 tricyclo<6.5.0.0^2,9>trideca-3,6,11-trien-5-one
  参考文献：
  名称：

  Through-Bond Interaction via Cyclobutane Relay Orbitals. Evaluation of the Question of Extended Conjugation in Belted [4,5]Dihomotropones

  摘要：

  The preparation of tricyclo[6.5.0.0(2,9)]trideca-3,6,10,12-tetraen-5-one (3), its dihydro derivative 16, and the structurally related carbinol 17 has been successfully realized. In a companion synthesis of the lower homolog 4, an inability to effect the desulfonylative ring contraction either of 26 or 29 was encountered. Although introduction of the ethylene bridge could be accomplished first as in 23, the ease with which this ketal isomerized to 24 precluded its further use in the pursuit of 4. Molecular mechanics calculations showed the dienone subunit in 4 to deviate significantly from planarity. This behavior is in striking contrast to the planar minimum energy conformations computed for [4,5]dihomotropone (2) and its higher vinylog 3. An evaluation of the spectral properties of 3 reveal this ketone not to be polarized. No evidence that could be construed to be a reflection of ground-state through-bond interaction was uncovered.

  DOI：

  10.1021/jo00098a032
• 作为产物：
  描述：

  Methanesulfonic acid 4-oxo-1,2,3,4,5,5a,6,7,10,10a-decahydro-1,6-cyclo-heptalen-3-yl ester 在 三氟化硼乙醚 、 lithium bromide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 28.5h， 生成 ethyl 6-bromo-5-oxotricyclo<6.5.0.0^2,9>tridec-11-ene-4-carboxylate
  参考文献：
  名称：

  Through-Bond Interaction via Cyclobutane Relay Orbitals. Evaluation of the Question of Extended Conjugation in Belted [4,5]Dihomotropones

  摘要：

  The preparation of tricyclo[6.5.0.0(2,9)]trideca-3,6,10,12-tetraen-5-one (3), its dihydro derivative 16, and the structurally related carbinol 17 has been successfully realized. In a companion synthesis of the lower homolog 4, an inability to effect the desulfonylative ring contraction either of 26 or 29 was encountered. Although introduction of the ethylene bridge could be accomplished first as in 23, the ease with which this ketal isomerized to 24 precluded its further use in the pursuit of 4. Molecular mechanics calculations showed the dienone subunit in 4 to deviate significantly from planarity. This behavior is in striking contrast to the planar minimum energy conformations computed for [4,5]dihomotropone (2) and its higher vinylog 3. An evaluation of the spectral properties of 3 reveal this ketone not to be polarized. No evidence that could be construed to be a reflection of ground-state through-bond interaction was uncovered.

  DOI：

  10.1021/jo00098a032