2,3-dioxabicyclo[2.2.2]ocz-7-en-5-one | 301849-82-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-dioxabicyclo[2.2.2]ocz-7-en-5-one
• 英文别名: 2,3-dioxabicyclo[2.2.2]oct-7-en-5-one
• CAS: 301849-82-1
• 化学式: C₆H₆O₃
• 分子量: 126.112
• InChiKey: OFMZYNHUQOBMMV-UHFFFAOYSA-N

物化性质

• 沸点：
  190.3±40.0 °C(Predicted)
• 密度：
  1.329±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.21
• 重原子数：
  9.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2,3-dioxabicyclo[2.2.2]ocz-7-en-5-one 在 potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 以10%的产率得到苯酚
  参考文献：
  名称：

  2,3-Dioxabicyclo[2.2.2]oct-7-en-5-one:  Synthesis and Reactions of the Keto Endoperoxide of Phenol

  摘要：

  The photooxygenation of 1,4-cyclohexadiene (3) affords the diastereomeric hydroperoxy endoperoxides exo-4 and endo-4 and the diastereomeric hydroperoxides trans-5 and cis-5 in a ratio of 87: 9:3.5:0.5. Selective reduction of hydroperoxide group in the endoperoxides exo-4 and endo-4 in the presence of titanium tetraisopropoxide-diethyl sulfide gave the corresponding hydroxy endoperoxides exo-7 and endo-7, which on PCC oxidation leads to the phenol-derived keto endoperoxide 2. The triphenylphosphine deoxygenation of the keto endoperoxide 2 produces a 9:1 mixture of 1,2- and 1,4-dihydroxybenzenes 10 and 11, while the CoTPP-catalyzed rearrangement affords the bisepoxide 12, malealdehyde (13), and beta-lactone 14. The mechanisms of these transformations are presented.

  DOI：

  10.1021/jo000120p
• 作为产物：
  描述：

  endo-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide 在 titanium(IV) isopropylate 、 乙硫醚 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 3.08h， 生成 2,3-dioxabicyclo[2.2.2]ocz-7-en-5-one
  参考文献：
  名称：

  2,3-Dioxabicyclo[2.2.2]oct-7-en-5-one:  Synthesis and Reactions of the Keto Endoperoxide of Phenol

  摘要：

  The photooxygenation of 1,4-cyclohexadiene (3) affords the diastereomeric hydroperoxy endoperoxides exo-4 and endo-4 and the diastereomeric hydroperoxides trans-5 and cis-5 in a ratio of 87: 9:3.5:0.5. Selective reduction of hydroperoxide group in the endoperoxides exo-4 and endo-4 in the presence of titanium tetraisopropoxide-diethyl sulfide gave the corresponding hydroxy endoperoxides exo-7 and endo-7, which on PCC oxidation leads to the phenol-derived keto endoperoxide 2. The triphenylphosphine deoxygenation of the keto endoperoxide 2 produces a 9:1 mixture of 1,2- and 1,4-dihydroxybenzenes 10 and 11, while the CoTPP-catalyzed rearrangement affords the bisepoxide 12, malealdehyde (13), and beta-lactone 14. The mechanisms of these transformations are presented.

  DOI：

  10.1021/jo000120p