| 130670-19-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 130670-19-8
• 化学式: C₂₁H₂₂O₃
• 分子量: 322.404
• InChiKey: NIHVYMJCBUAUJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.83
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  在 苯甲酸 作用下， 反应 4.0h， 以95%的产率得到homocubylidenehomocubane
  参考文献：
  名称：

  Pinacol condensation of homocubanone. Synthesis and chemistry of homocubylidenehomocubane

  摘要：

  Reductive coupling of homocubanone (1) with TiCl4-Zn afforded the corresponding pinacol (3, 21%) and homocubanol (4, 40%). Reaction of 3 with HC(OEt)3 in the presence of benzoic acid afforded cyclic orthoformate 5 (95%), which when heated with benzoic acid at 200-degrees-C gave homocubylidenehomocubane (2, 95%). When treated with AgNO3-impregnated silica gel at 25-degrees-C for 6 days, 2 gradually underwent homocubane-norsnoutane rearrangement, thereby affording 7. Acid-promoted pinacol rearrangement of 3 gave the corresponding pinacolone 6 (61%). Electrophilic addition of trifluoroacetic acid and of bromine to the C=C double bond in 2 proceeded in both cases via simple 1,2-addition (i.e., without accompanying Wagner-Meerwein rearrangement), thereby affording 8 (64%) and 9 (24%), respectively. The structures of 2, 6, 7, and 9 were elucidated via X-ray crystallographic methods. The results of MM2 calculations suggest that there is insufficient driving force provided by relief of steric strain to promote Wagner-Meerwein rearrangement of the carbocation that is produced upon protonation of the C=C double bond in 2.

  DOI：

  10.1021/jo00001a054
• 作为产物：
  描述：

  9-<9'-hydroxy-9'-homocubyl>homocuban-9-ol 、 原甲酸三乙酯 在 苯甲酸 作用下， 反应 3.0h， 以95%的产率得到
  参考文献：
  名称：

  Pinacol condensation of homocubanone. Synthesis and chemistry of homocubylidenehomocubane

  摘要：

  Reductive coupling of homocubanone (1) with TiCl4-Zn afforded the corresponding pinacol (3, 21%) and homocubanol (4, 40%). Reaction of 3 with HC(OEt)3 in the presence of benzoic acid afforded cyclic orthoformate 5 (95%), which when heated with benzoic acid at 200-degrees-C gave homocubylidenehomocubane (2, 95%). When treated with AgNO3-impregnated silica gel at 25-degrees-C for 6 days, 2 gradually underwent homocubane-norsnoutane rearrangement, thereby affording 7. Acid-promoted pinacol rearrangement of 3 gave the corresponding pinacolone 6 (61%). Electrophilic addition of trifluoroacetic acid and of bromine to the C=C double bond in 2 proceeded in both cases via simple 1,2-addition (i.e., without accompanying Wagner-Meerwein rearrangement), thereby affording 8 (64%) and 9 (24%), respectively. The structures of 2, 6, 7, and 9 were elucidated via X-ray crystallographic methods. The results of MM2 calculations suggest that there is insufficient driving force provided by relief of steric strain to promote Wagner-Meerwein rearrangement of the carbocation that is produced upon protonation of the C=C double bond in 2.

  DOI：

  10.1021/jo00001a054