1-(2,2-dimethylpropoxy)-1-oxo-1λ5,2-benziodoxol-3-one | 185566-85-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(2,2-dimethylpropoxy)-1-oxo-1λ5,2-benziodoxol-3-one
• CAS: 185566-85-2
• 化学式: C₁₂H₁₅IO₄
• 分子量: 350.153
• InChiKey: YGWGABMODOTWKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-(2,2-dimethylpropoxy)-1-oxo-1λ5,2-benziodoxol-3-one 在 水 作用下， 以 氘代二甲亚砜 为溶剂， 生成 新戊醇 、 2-碘酰基苯甲酸
  参考文献：
  名称：

  Hypervalent Iodine Oxidants:  Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-Iodoxybenzoic Acid (IBX) and Dess−Martin Periodinane. A Comparative ¹H-NMR Study

  摘要：

  Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by H-1-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d(6) solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison of the chemical shift difference data with those obtained for Dess-Martin periodinane (DMP)-alcoholate and -diolate adducts. The dichotomous behavior exhibited by IBX and DMP with 1,2-diols can be explained in terms of the different architecture of the reactive intermediates involved in the oxidation. With aliphatic alcohols, kinetic evidences support a two-step reaction mechanism involving a fast pre-equilibrium step leading to 5, followed by a rate-determining disproportionation step. With electronically activated benzyl alcohol, the attainment of preequilibrium is largely dependent on initial water concentration as a consequence of a particularly high k(2) value. The influence of the alcohol structure on measured equilibrium (K-eq) and rate constants (k(2)) and the effect of water on the overall reaction rate are discussed.

  DOI：

  10.1021/jo961044m
• 作为产物：
  描述：

  新戊醇 、 2-碘酰基苯甲酸 以 氘代二甲亚砜 为溶剂， 生成 1-(2,2-dimethylpropoxy)-1-oxo-1λ5,2-benziodoxol-3-one
  参考文献：
  名称：

  Hypervalent Iodine Oxidants:  Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-Iodoxybenzoic Acid (IBX) and Dess−Martin Periodinane. A Comparative ¹H-NMR Study

  摘要：

  Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by H-1-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d(6) solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison of the chemical shift difference data with those obtained for Dess-Martin periodinane (DMP)-alcoholate and -diolate adducts. The dichotomous behavior exhibited by IBX and DMP with 1,2-diols can be explained in terms of the different architecture of the reactive intermediates involved in the oxidation. With aliphatic alcohols, kinetic evidences support a two-step reaction mechanism involving a fast pre-equilibrium step leading to 5, followed by a rate-determining disproportionation step. With electronically activated benzyl alcohol, the attainment of preequilibrium is largely dependent on initial water concentration as a consequence of a particularly high k(2) value. The influence of the alcohol structure on measured equilibrium (K-eq) and rate constants (k(2)) and the effect of water on the overall reaction rate are discussed.

  DOI：

  10.1021/jo961044m