3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane | 1599480-46-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane
• 英文别名: 3-Tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane
• CAS: 1599480-46-2
• 化学式: C₁₆H₃₄O₄Si₂
• 分子量: 346.615
• InChiKey: NOUZLRUYHBVHSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane 在 三苯基膦 作用下， 以 乙醚 为溶剂， 反应 8.0h， 以73%的产率得到3-tert-butyl-8,8,11,11-tetramethyl-7,12-dioxa-8,11-disilaspiro-[5.6]dodecane
  参考文献：
  名称：

  减少有机硅过氧化物：环收缩和环二聚化

  摘要：

  The reduction of 1,7,8-tetraoxa-3,6-disilonanes is accompanied by the selective transformation of two SiOOC moieties into SiOC moieties, resulting in contraction of the nine-membered ring bis-peroxide to a previously unknown class of seven-membered-ring acetals, 1,6-dioxa-2,5-disilepanes. The reduction of six-membered cyclic peroxide proceeds differently and affords four- and eight-membered rings. As a result, silyl ethers of gem-diols; which do not exist in the free form, are produced.

  DOI：

  10.1021/acs.organomet.6b00129
• 作为产物：
  描述：

  1,2-双(氯二甲基硅基)乙烷 、 1,1-dihydroperoxy-(4-tert-butyl)cyclohexane 在 咪唑 作用下， 以 乙醚 为溶剂， 反应 1.5h， 以95%的产率得到3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane
  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

文献信息

• Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides
  作者：Ashot V. Arzumanyan、Roman A. Novikov、Alexander O. Terent’ev、Maxim M. Platonov、Valentin G. Lakhtin、Dmitry E. Arkhipov、Alexander A. Korlyukov、Vladimir V. Chernyshev、Andrew N. Fitch、Alexander T. Zdvizhkov、Igor B. Krylov、Yury V. Tomilov、Gennady I. Nikishin

  DOI：10.1021/om500095x

  日期：2014.5.12

  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.
• Reduction of Organosilicon Peroxides: Ring Contraction and Cyclodimerization
  作者：Ashot V. Arzumanyan、Alexander O. Terent’ev、Roman A. Novikov、Valentin G. Lakhtin、Michail S. Grigoriev、Gennady I. Nikishin

  DOI：10.1021/acs.organomet.6b00129

  日期：2016.6.13

  The reduction of 1,7,8-tetraoxa-3,6-disilonanes is accompanied by the selective transformation of two SiOOC moieties into SiOC moieties, resulting in contraction of the nine-membered ring bis-peroxide to a previously unknown class of seven-membered-ring acetals, 1,6-dioxa-2,5-disilepanes. The reduction of six-membered cyclic peroxide proceeds differently and affords four- and eight-membered rings. As a result, silyl ethers of gem-diols; which do not exist in the free form, are produced.