2,4-Di-tert-butyl-2,4-bis-(2,4,6-trimethyl-phenyl)-[1,3,2,4]dioxadisiletane | 89486-30-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2,4-Di-tert-butyl-2,4-bis-(2,4,6-trimethyl-phenyl)-[1,3,2,4]dioxadisiletane
• 英文别名: Di-t-butyldimesitylcyclodisiloxane；2,4-ditert-butyl-2,4-bis(2,4,6-trimethylphenyl)-1,3,2,4-dioxadisiletane
• CAS: 89486-30-6
• 化学式: C₂₆H₄₀O₂Si₂
• 分子量: 440.773
• InChiKey: JUFPJCKQTUBPLU-UHFFFAOYSA-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 以 甲苯 为溶剂， 生成 2,4-Di-tert-butyl-2,4-bis-(2,4,6-trimethyl-phenyl)-[1,3,2,4]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

文献信息

• Formation of a disiloxirane in the oxidation of 1,2-dimesityl-1,2-di-t-butyldisilaethylene
  作者：Michael J. Michalczyk、Robert West、Josef Michl

  DOI：10.1039/c39840001525

  日期：——

  Reaction of trans-1,2-di-t-butyl-1,2-dimesityldisilaethylene in solution with dioxygen at –78 °C produces the disiloxirane (7) and a compound believed to be the 1,2-disiladioxetane (8a); the latter compound rearranges quantitatively to the known 1,3-cyclodisiloxane (5) above 0 °C.

  在–78°C下，溶液中的反式-1,2-二叔丁基-1，2-二甲苯基二硅烷基乙烯与双氧反应生成二硅氧烷基（7）和一种化合物，被认为是1,2-二硅基二氧杂环丁烷（8a）；后一种化合物在0°C以上定量重排为已知的1,3-环二硅氧烷（5）。
• MICHALCZYK, M. J.;WEST, R.;MICHL, J., J. CHEM. SOC. CHEM. COMMUN., 1984, N 22, 1525-1526
  作者：MICHALCZYK, M. J.、WEST, R.、MICHL, J.

  DOI：——

  日期：——