3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradec-10-yne | 1599480-61-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradec-10-yne
• CAS: 1599480-61-1
• 化学式: C₁₆H₃₀O₄Si₂
• 分子量: 342.583
• InChiKey: RNFMWHJMVPUTJN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  22.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  2,5-二氯-2,5-二甲基-2,5-二硅杂-3-己炔 、 1,1-dihydroperoxy-(4-tert-butyl)cyclohexane 在 咪唑 作用下， 以 乙醚 为溶剂， 以40%的产率得到3,18,32-tri-tert-butyl-9,9,12,12,23,23,26,26,37,37,40,40-dodecamethyl-7,8,13,14,21,22,27,28,35,36,41,42-dodecaoxa-9,12,23,26,37,40-hexasilatrispiro[5.8.5¹⁵.8.5²⁹.8⁶]dotetraconta-10,24,38-triyne
  参考文献：
  名称：

  Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides

  摘要：

  The reactions of 1,2-bis(dimethylchlorosilyl)ethane (1), 1,2-bis(dimethylchlorosilyl)ethene (6), and 1,2-bis(dimethylchlorosilyl)ethyne (7) with gem-bis-(hydroperoxides) 2a-h and 1,1'-bis( hydroperoxy)bis-(cycloalkyl)peroxides 4a-c were found to proceed in an unusual way. Thus, the reactions do not give the expected polymeric peroxides; instead, they produce cyclic silicon-containing peroxides containing 2, 4, or 6 silicon atoms in the ring: 9- (3a-h), 12- (5a-c), 18- (8, 12), 24- (9, 10), 27- (13), and 36-membered (11) compounds. The size of the rings produced in the reactions increases in the series 1,2-bis(dimethylchlorosilyl)ethane < 1,2-bis(dimethylchlorosilyl)ethene < 1,2-bis(dimethylchlorosilyl)ethyne. The resulting 9- and 12-membered cyclic peroxides are stable under ambient conditions. These compounds were isolated by chromatography and characterized by H-1, C-13, and Si-29 NMR spectroscopy, X-ray diffraction, elemental analysis, and high-resolution mass spectrometry. The yields vary from 77 to 95%. Structures of the larger-size rings (18-, 24-, 27-, and 36-membered peroxides) were confirmed by H-1, C-13, and Si-29 NMR spectroscopy using 2D (COSY, HSQC, and HMBC), 2D DOSY H-1, 3D H-1-Si-29 HMBC-DOSY NMR experiments, and elemental analysis.

  DOI：

  10.1021/om500095x