cis-2,2-Dichloro-4-methoxy-2,2a,7,7a-tetrahydrocyclobutainden-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: cis-2,2-Dichloro-4-methoxy-2,2a,7,7a-tetrahydrocyclobutainden-1-one
• 英文别名: cis-2,2-Dichloro-4-methoxy-2,2a,7,7a-tetrahydrocyclobuta[a]inden-1-one；(2aS,7aS)-2,2-dichloro-4-methoxy-7,7a-dihydro-2aH-cyclobuta[a]inden-1-one
• 化学式: C₁₂H₁₀Cl₂O₂
• 分子量: 257.116
• InChiKey: PVKPKJHDCWKUNC-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-2,2-Dichloro-4-methoxy-2,2a,7,7a-tetrahydrocyclobutainden-1-one 在 palladium on activated charcoal 吡啶 、 lithium aluminium tetrahydride 、 氢气 、 溶剂黄146 、 锌 作用下， 以 甲醇 、 乙醚 为溶剂， -20.0~180.0 ℃ 、2.67 kPa 条件下， 反应 25.5h， 生成 cis-5-Methoxy-1,2,3,3a,8,8a-hexahydrocyclopentaindene
  参考文献：
  名称：

  Synthesis and Structure Analysis of a Linear Benzannulated Cis-Cisoid-Cis Tetraquinane

  摘要：

  Contrary to expectations, the photoreaction of the benzannulated bicyclo[3.3.0] octene 9 with 2-cyclohexene-1,4-dione (12) leads to a [2 + 2] cycloaddition preferentially on the endo- rather than on the exo-side. Upon treatment with trimethylsilyl iodide, the major compound 14 rearranges to 16 with a cis-cisoid-cis triquinane structure. The X-ray structure analysis of 16 revealed a ''closed'' U-type geometry. The fact that 16 shows different conformations in solution and the solid state is interpreted in terms of a partial pseudorotation of the central cyclopentane ring. According to MM2 calculations, the barrier between the U-shaped and the ''opened'' conformation is about 10-12 kJ/ mol.

  DOI：

  10.1021/jo00084a045
• 作为产物：
  描述：

  5-甲氧基-1H-茚 、 三氯乙酰氯 在 铜 、 锌 、 三氯氧磷 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以89%的产率得到cis-2,2-Dichloro-4-methoxy-2,2a,7,7a-tetrahydrocyclobutainden-1-one
  参考文献：
  名称：

  Synthesis and Structure Analysis of a Linear Benzannulated Cis-Cisoid-Cis Tetraquinane

  摘要：

  Contrary to expectations, the photoreaction of the benzannulated bicyclo[3.3.0] octene 9 with 2-cyclohexene-1,4-dione (12) leads to a [2 + 2] cycloaddition preferentially on the endo- rather than on the exo-side. Upon treatment with trimethylsilyl iodide, the major compound 14 rearranges to 16 with a cis-cisoid-cis triquinane structure. The X-ray structure analysis of 16 revealed a ''closed'' U-type geometry. The fact that 16 shows different conformations in solution and the solid state is interpreted in terms of a partial pseudorotation of the central cyclopentane ring. According to MM2 calculations, the barrier between the U-shaped and the ''opened'' conformation is about 10-12 kJ/ mol.

  DOI：

  10.1021/jo00084a045

文献信息

• Synthesis and Structure Analysis of a Linear Benzannulated Cis-Cisoid-Cis Tetraquinane
  作者：Rolf Aebi、Wolfgang Luef、Reinhart Keese

  DOI：10.1021/jo00084a045

  日期：1994.3

  Contrary to expectations, the photoreaction of the benzannulated bicyclo[3.3.0] octene 9 with 2-cyclohexene-1,4-dione (12) leads to a [2 + 2] cycloaddition preferentially on the endo- rather than on the exo-side. Upon treatment with trimethylsilyl iodide, the major compound 14 rearranges to 16 with a cis-cisoid-cis triquinane structure. The X-ray structure analysis of 16 revealed a ''closed'' U-type geometry. The fact that 16 shows different conformations in solution and the solid state is interpreted in terms of a partial pseudorotation of the central cyclopentane ring. According to MM2 calculations, the barrier between the U-shaped and the ''opened'' conformation is about 10-12 kJ/ mol.