tricyclo<6.5.0.0^2,9>tridec-11-en-5-one | 159145-56-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tricyclo<6.5.0.0^2,9>tridec-11-en-5-one
• 英文别名: Tricyclo[6.5.0.02,9]tridec-11-en-5-one
• CAS: 159145-56-9
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: VKOBDNIEIFRUFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tricyclo<6.5.0.0^2,9>tridec-11-en-5-one 在 硫酸 、 potassium tert-butylate 、 溴 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 乙二醇 、 苯 为溶剂， 反应 51.5h， 生成 tricyclo<6.5.0.0^2,9>trideca-3,6,10,12-tetraen-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：

  5-Oxo-tricyclo[6.5.0.0^2,9]tridec-11-ene-4-carboxylic acid ethyl ester 在 盐酸 作用下， 以 丙酮 为溶剂， 反应 4.0h， 生成 tricyclo<6.5.0.0^2,9>tridec-11-en-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

文献信息

• Through-Bond Interaction via Cyclobutane Relay Orbitals. Evaluation of the Question of Extended Conjugation in Belted [4,5]Dihomotropones
  作者：Leo A. Paquette、Timothy J. Watson

  DOI：10.1021/jo00098a032

  日期：1994.9

  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.