2-Chloro-2-oxoethaneperoxoic acid | 873450-69-2

• 英文名称: 2-Chloro-2-oxoethaneperoxoic acid
• CAS: 873450-69-2
• 化学式: C₂HClO₄
• 分子量: 124.481
• InChiKey: MICQJJAJMVBCAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  草酰氯 在 双氧水 作用下， 以 乙酸乙酯 为溶剂， 生成 2-Chloro-2-oxoethaneperoxoic acid
  参考文献：
  名称：

  Direct Kinetic Observation of the Chemiexcitation Step in Peroxyoxalate Chemiluminescence

  摘要：

  A high-energy intermediate in the peroxyoxalate reaction can be accumulated at room temperature under specific reaction conditions and in the absence of any reducing agent in up to micromolar concentrations. Bimolecular interaction of this intermediate, accumulated in the reaction of oxalyl chloride with hydrogen peroxide, with an activator (highly fluorescent aromatic hydrocarbons with low oxidation potential) added in delay shows unequivocally that this intermediate is responsible for chemiexcitation of the activator. Activation parameters for the unimolccular decomposition of this intermediate (Delta H-double dagger = 11.2 kcal mol(-1); Delta S-double dagger = -23.2 cal mol(-1) K-1) and for its bimolecular reaction with 9,10-diphenylanthracene (Delta H-double dagger = 4.2 kcal mol(-1); Delta S-double dagger = -26.9 cal mol(-1) K-1) show that this intermediate is much less stable than typical 1,2-dioxetanes and 1,2-dioxetanones and demonstrate its highly favored interaction with the activator. Therefore, it can be inferred that structural characterization of the high-energy intermediate in the presence of an activator must be highly improbable. The observed linear free-energy correlation between the catalytic rate constants and the oxidation potentials of several activators definitely confirms the occurrence of the chemically initiated electron-exchange luminescence (CIEEL) mechanism in the chemiexcitation step of the peroxyoxalate system.

  DOI：

  10.1021/jo901402k