1-benzoxy-1H-1λ³-benzo[d][1,2]iodoxol-3-one | 52399-80-1

• 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-benzoxy-1H-1λ³-benzo[d][1,2]iodoxol-3-one
• 英文别名: (3-Oxo-1lambda3,2-benziodoxol-1-yl) benzoate；(3-oxo-1λ3,2-benziodoxol-1-yl) benzoate
• CAS: 52399-80-1
• 化学式: C₁₄H₉IO₄
• 分子量: 368.128
• InChiKey: JPMVIWIWJUSFDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-羟基-1,2-苯碘酰-3(1H)-酮 以 氯仿 为溶剂， 45.0 ℃ 、4.67 kPa 条件下， 反应 0.08h， 生成 1-benzoxy-1H-1λ³-benzo[d][1,2]iodoxol-3-one
  参考文献：
  名称：

  Solution Structure of Some λ³ Iodanes:  An ¹⁷O NMR and DFT Study

  摘要：

  The structure of a series of I-O bonded bis(acyloxy)iodoarenes and benzoiodoxolones in chloroform solution has been investigated by O-17 NMR spectroscopy and by density functional theory (DFT) calculations, employing the PBE0 functional together with the LANL2DZ basis set extended with polarization (d) and diffuse (p) functions. This combined approach allowed us to ascertain that, although these classes of lambda(3) iodanes maintain in chloroform solution their solid state "T-shaped" structure, a degenerate [1,3] sigmatropic shift of iodine between the two oxygens of the acyloxy groups occurs in solution. The energy barrier involved in this process differs in the two classes, thus causing significant differences in the O-17 NMR spectra, at room temperature, of the two classes of compounds.

  DOI：

  10.1021/jo070111h

文献信息

• Kinetics and mechanisms of the reactions of benzoyl derivatives of nucleophiles: dependence of the solvation requirement of the reaction on the structures of the nucleophile and the acyl group
  作者：Omar A. El Seoud、Monica Ferreira、Wagner A. Rodrigues、Marie-Fran�oise Ruasse

  DOI：10.1002/poc.864

  日期：2005.2

  desolvation of the entering nucleophile contribute to the OH−-mediated reaction; (ii) the negative and positive signs of ΔS≠ indicate large differences in solvation of the transition states of the kO and kOH pathways. For the spontaneous decomposition of ArCO-Phos, sizeable substituent effects on both ΔH≠ and ΔS≠ were observed. This shows the contribution of solvation of the leaving benzoate and substituent-induced

  研究了亲核试剂的两个系列苯甲酰基衍生物的反应，并将其与N-苯并咪唑的反应结果进行了比较。通用结构为ArCO-Nu，其中Ar ＝ XC 6 H 4-和/或X 2 -C 6 H 3-；X ＝ 4-Me，H，4-Cl，4-CN，4-NO 2，X 2  ＝ 3，5-二硝基。Nu =碘代苯甲酸酯ArCO-Iba和磷酸二阴离子ArCO-Phos。催化速率常数，动力学溶剂同位素效应，动力学取代基效应（哈米特方程）和Δ的依赖性ħ ≠和Δ小号≠上σ X被确定。对于ArCO-Iba，水解通过两条途径发生，即未催化的（k O）和特定的碱催化的（k OH）水攻击碘代苯甲酸酯环的碘原子。该结论基于对ArCO-Iba上的部分电荷的理论计算，以及分别在25°C，k O和k OH下于-0.22和0.92处计算出的小ρ值。ArCO-Phos反应的数据与解离过渡态一致，从而消除了偏磷酸单阴离子（PO）。讨论了机理途径对亲核试剂的依赖性。两个结果是相关的ARCO