3,4-ditert-butyl-3,4-bis(2,4,6-trimethylphenyl)(1,2-18O2)dioxadisiletane | 141396-69-2

• 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: 3,4-ditert-butyl-3,4-bis(2,4,6-trimethylphenyl)(1,2-18O2)dioxadisiletane
• CAS: 141396-69-2
• 化学式: C₂₆H₄₀O₂Si₂
• 分子量: 444.775
• InChiKey: VKEPGUCUQMREQZ-HNVFEQMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.18
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (E)-1,2-di-tert-butyl-1,2-dimesityl-1,2-disiladioxetane 在 <18>O2 作用下， 以 正己烷 为溶剂， 反应 4.5h， 生成 3,4-ditert-butyl-3,4-bis(2,4,6-trimethylphenyl)(1,2-18O2)dioxadisiletane
  参考文献：
  名称：

  1,2-Disiladioxetanes: structure, rearrangement and reactivity

  摘要：

  The low-temperature reaction of (E)-1,2-dimesityl-1,2-di-tert-butyldisilene (1a) with dioxygen gives (E)-1,2-dimesityl-1,2-di-tert-butyldisiladioxetane (2a), the structure of which has been established by X-ray crystallographic analysis. This result establishes that both oxidation of la and rearrangement of 2a to 1,3-cyclodisiloxane 4a take place with retention of configuration at silicon. Disiladioxetane 2a forms monoclinic crystals, space group C2/c. Extra electron density found above and below the Si-Si bond was shown by H-1 and solid-state Si-29 NMR to be due to 4a, arising from rearrangement of 2a in the solid. X-ray crystal structures were determined for crystals that were 5.6%, 15.2%, and 20.3% rearranged. Cell dimensions for the 5.6% rearranged crystal are a = 12.549 (7) angstrom, b = 12.174 (7) angstrom, c = 17.133 (7) angstrom, b = 103.94 (4)-degrees, V = 2529 (2) angstrom3 (Z = 4). The rearrangement of 2a in solution is first order with E(a) = +21.7 +/- 1.0 kcal mol-1, DELTA-H(double dagger) = 21.1 +/- 1.4 kcal mol-1, and DELTA-S(double dagger) = -9.0 +/- 4.5 cal K-1 mol-1. Isotope labeling studies with O-18 showed the rearrangement to be intramolecular in the solid and in solution. In the presence of phosphines or sulfides, 2a is partially deoxygenated to form disilaoxirane 3a.

  DOI：

  10.1021/ja00039a035