endo-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: endo-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide
• 英文别名: 7-Hydroperoxy-2,3-dioxabicyclo[2.2.2]oct-5-ene；7-hydroperoxy-2,3-dioxabicyclo[2.2.2]oct-5-ene
• 化学式: C₆H₈O₄
• 分子量: 144.127
• InChiKey: DUTLUPDASWGHSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  endo-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide 在 titanium(IV) isopropylate 、 乙硫醚 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以95%的产率得到endo-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol
  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：

  1,4-环己二烯 在 5,10,15,20-tetrakisphenylporphyrin 、 氧气 作用下， 以 氯仿 为溶剂， 反应 24.0h， 以69%的产率得到endo-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide
  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

文献信息

• 2,3-Dioxabicyclo[2.2.2]oct-7-en-5-one:  Synthesis and Reactions of the Keto Endoperoxide of Phenol
  作者：Waldemar Adam、Metin Balci、Hamdullah Kiliç

  DOI：10.1021/jo000120p

  日期：2000.9.1

  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.