9-<9'-(trifluoroacetoxy)-9'-homocubyl>homocubane | 130670-22-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 9-<9'-(trifluoroacetoxy)-9'-homocubyl>homocubane
• 英文别名: [9-(9-Pentacyclo[4.3.0.02,5.03,8.04,7]nonanyl)-9-pentacyclo[4.3.0.02,5.03,8.04,7]nonanyl] 2,2,2-trifluoroacetate；[9-(9-pentacyclo[4.3.0.02,5.03,8.04,7]nonanyl)-9-pentacyclo[4.3.0.02,5.03,8.04,7]nonanyl] 2,2,2-trifluoroacetate
• CAS: 130670-22-3
• 化学式: C₂₀H₁₇F₃O₂
• 分子量: 346.349
• InChiKey: PSYXGOWTIUWLFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  homocubylidenehomocubane 、 三氟乙酸 以 氯仿 为溶剂， 反应 6.0h， 以64%的产率得到9-<9'-(trifluoroacetoxy)-9'-homocubyl>homocubane
  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

文献信息

• Pinacol condensation of homocubanone. Synthesis and chemistry of homocubylidenehomocubane
  作者：Alan P. Marchand、V. Vidyasagar、William H. Watson、Ante Nagl、Ram P. Kashyap

  DOI：10.1021/jo00001a054

  日期：1991.1

  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.