| 134736-32-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 134736-32-6；134780-14-6
• 化学式: C₁₅H₃₂O₅Si
• 分子量: 320.502
• InChiKey: FHXGYKQARNLBNN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  叔丁乙酸甲酯 在 1,1,1-三氟丙酮 六甲基磷酰三胺 、 正丁基锂 、 氧气 、 tetraphenylporphyrin 、 乙醛 、 异丙胺 作用下， 以 四氯化碳 为溶剂， 反应 6.67h， 生成
  参考文献：
  名称：

  Photooxygenation of silyl ketene acetals: dioxetanes as precursors to .alpha.-silylperoxy esters in the silatropic ene reaction

  摘要：

  Photooxygenation of silyl ketene acetals afforded dioxetanes, which subsequently underwent secondary reactions to give rearrangement products (alpha-silylperoxy esters, major products) and cleavage products (pivalaldehyde, minor product). The kinetics of these reactions were studied by NMR and chemiluminescence. The activation energy of the chemiluminescent cleavage process was 2-3 kcal/mol higher than that of the rearrangement. In the presence of catalytic amounts of CF3COCF3 or CF3COCH3, the (E)-silyl ketene acetals rearranged into their Z isomers. Photooxygenation of the (E)- and (Z)-silyl ketene acetals showed that the [2 + 2] cycloaddition was rigorously diastereoselective. Trapping experiments with acetaldehyde confirmed the intermediacy of 1,4-zwitterions in the rearrangement of the (E)- and (Z)-dioxetanes into alpha-silylperoxy esters, but such intermediates were not detected during the photooxygenation of the silyl ketene acetals; the latter proceeds presumably via perepoxides.

  DOI：

  10.1021/jo00015a030