3,3-dimethylbicyclo[3.2.2]nonane | 204504-83-6

• 分子结构分类: 有机化合物 - 碳氢化合物
• 英文名称: 3,3-dimethylbicyclo[3.2.2]nonane
• CAS: 204504-83-6
• 化学式: C₁₁H₂₀
• 分子量: 152.28
• InChiKey: AIPBGPNTMMWVNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,3-dimethylbicyclo[3.2.2]nonane 在 chromium(VI) oxide 、 lithium aluminium tetrahydride 、 乙酸酐 、 溶剂黄146 作用下， 生成 3,3-dimethylbicyclo[3.2.2]nonan-1-ol
  参考文献：
  名称：

  Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:  Evaluation of π-Conjugative Stabilization of α-Thiocarbonyl Carbocations

  摘要：

  The ethanolysis rates of 3,3-dimethyl-2-thioxobicyclo[2.2.2]oct-1 triflate and 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl triflate relative to their corresponding parent compounds (3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate and 3,3-dimethylbicyclo[3.2.2]non-1-yl triflate, respectively) at 25.0 degrees C increase from 10(-6.2) to 10(-2.5). The increase in the rate ratios with the flexibility of the ring system supports the applicability of the authors' methodology to change the conjugative ability of bridgehead carbocations. Formation of 3,3-dimethyl-1,2-epithio-2-ethoxybicyclo[3.2.2]nonane in the ethanolysis of 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl 2,2,2-trifluoroethanesulfonate indicates cyclization of the intermediate 3,3-dimethyl-2-thioxobicyclo[3.2.2]nonyl cation into an episulfide cation. Computational studies at the HF/6-31G* level indicate that the resonance interaction between the cationic center and the C=S pi system is greater in the 3,3-dimethyl-2-thioxobicyclo[3.2,2]nonyl cation than in the 3,3-dimethyl-2-thioxobicyclo[2.2.2]octyl cation.

  DOI：

  10.1021/jo9719564
• 作为产物：
  描述：

  3,3-dimethylbicyclo[3.2.2.]nonan-2-one 在 氢氧化钾 、 一水合肼 作用下， 以 various solvent(s) 为溶剂， 以18%的产率得到3,3-dimethylbicyclo[3.2.2]nonane
  参考文献：
  名称：

  Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:  Evaluation of π-Conjugative Stabilization of α-Thiocarbonyl Carbocations

  摘要：

  The ethanolysis rates of 3,3-dimethyl-2-thioxobicyclo[2.2.2]oct-1 triflate and 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl triflate relative to their corresponding parent compounds (3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate and 3,3-dimethylbicyclo[3.2.2]non-1-yl triflate, respectively) at 25.0 degrees C increase from 10(-6.2) to 10(-2.5). The increase in the rate ratios with the flexibility of the ring system supports the applicability of the authors' methodology to change the conjugative ability of bridgehead carbocations. Formation of 3,3-dimethyl-1,2-epithio-2-ethoxybicyclo[3.2.2]nonane in the ethanolysis of 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl 2,2,2-trifluoroethanesulfonate indicates cyclization of the intermediate 3,3-dimethyl-2-thioxobicyclo[3.2.2]nonyl cation into an episulfide cation. Computational studies at the HF/6-31G* level indicate that the resonance interaction between the cationic center and the C=S pi system is greater in the 3,3-dimethyl-2-thioxobicyclo[3.2,2]nonyl cation than in the 3,3-dimethyl-2-thioxobicyclo[2.2.2]octyl cation.

  DOI：

  10.1021/jo9719564