1,1,3,3-tetramesityl-1,3-cyclodisiloxane | 84537-22-4

• 分子结构分类: 有机化合物
• 英文名称: 1,1,3,3-tetramesityl-1,3-cyclodisiloxane
• 英文别名: tetramesityldisiloxane；tetramesitylcyclodisiloxane；2,2,4,4-Tetramesitylcyclodisiloxane；2,2,4,4-tetrakis(2,4,6-trimethylphenyl)-1,3,2,4-dioxadisiletane
• CAS: 84537-22-4
• 化学式: C₃₆H₄₄O₂Si₂
• 分子量: 564.915
• InChiKey: GREXOYUMMMHMMD-UHFFFAOYSA-N

物化性质

• 沸点：
  594.3±60.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.25
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,1,3,3-tetramesityl-1,3-cyclodisiloxane 在 水 、 lithium dihydronaphthylide radical 作用下， 生成 Tetrakis(2,4,6-trimethylphenyl)disilane-1,2-diol
  参考文献：
  名称：

  Tetramesitylcyclodisiloxane: a cyclic siloxane with an unusual structure

  摘要：

  DOI：

  10.1021/ja00315a077
• 作为产物：
  描述：

  1,1,2,2-tetramesityl-1,2-disiladioxetane 以 甲苯 为溶剂， 以23 mg的产率得到1,1,3,3-tetramesityl-1,3-cyclodisiloxane
  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

• Molecular interactions of polysilane and unsaturated nitrogen compounds. Photochemical addition of disilene versus silylene to azobenzene
  作者：Akihito Sakakibara、Yoshio Kabe、Toshio Shimizu、Wataru Ando

  DOI：10.1039/c39910000043

  日期：——

  Photochemical reaction of hexamesitylcyclotrisilane 1 or tetramesityldisilene 2 with azobenzene produces silanol 5via hydrolysis of diazasilacyclopropane 3 and/or 1,2-diaza-3,4-disilacyclobutane 4; the structure of 4 has been confirmed by variable temperature 1H NMR spectroscopy and single-crystal X-ray diffraction, the existence of an Si2N2 ring system is demonstrated.

  hexamesitylcyclotrisilane的光化学反应1或tetramesityldisilene 2与偶氮苯产生硅烷醇基5经由diazasilacyclopropane的水解3和/或1,2-二氮杂-3,4- disilacyclobutane 4 ; 通过可变温度1 H NMR光谱和单晶X射线衍射确认了4的结构，证明了Si 2 N 2环系统的存在。
• 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）。
• Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ-O)Si(OH)Mes₂Towards Water and Ether Molecules
  作者：Philipp Roesch、Ulrike Warzok、Martin Enke、Robert Müller、Caspar Schattenberg、Christoph A. Schalley、Martin Kaupp、Thomas Braun、Philipp Wittwer

  DOI：10.1002/chem.201702393

  日期：2017.10.9

  with tetramesitylsiloxanediol – the phase is important: The reactivity of the sterically demanding siloxanediol towards water and ether molecules differs drastically when reactions in solution, the solid state and the gas phase were investigated. Isotopic labelling of oxygen atoms (17O, 18O) revealed no exchange or interaction with water in solution, but [Mes2Si(18OH)(μ-18O)Si(18O)Mes2]− reacted in

  H 2 O与四甲硅烷基硅氧烷二醇相互作用–该相很重要：研究溶液，固态和气相中的反应时，对空间要求高的硅氧烷二醇对水和醚分子的反应性显着不同。氧原子的同位素标记（17 O，18 O）揭示了与水在溶液中没有交流或交互，但[的Mes 2的Si（18 OH）（μ- 18 O）的Si（18 O）的Mes 2 ] -的气体中进行反应阶段。
• Singlet oxygenation of oxadisiliranes. Syntheses and crystal structure of 1,2,4,3,5-trioxadisilolanes
  作者：Wataru Ando、Masahiro Kako、Takeshi Akasaka、Yoshio Kabe

  DOI：10.1016/s0040-4039(00)97575-0

  日期：——

  Singlet oxygenation of 2,2,3,3-tetraaryloxadisiliranes 1a-d gives the corresponding 1,2,4,3,5-trioxadisilolanes 2a-d, derivatives of a novel class of cyclic peroxides. The reaction mechanism is discussed in terms of possible peroxonium ion intermediate 6a as a nucleophilic oxidizing species.

  2,2,3,3-四芳基恶二硅环酮1a-d的单线态氧合得到相应的1,2,4,3,5-三恶二硅环酮2a-d，这是一类新型的环状过氧化物的衍生物。关于可能的过氧鎓离子中间体6a作为亲核性氧化物质，讨论了反应机理。
• Chemical reactions of tetramesityldisilene
  作者：Mark J. Fink、Douglas J. De Young、Robert West、Josef Michl

  DOI：10.1021/ja00342a079

  日期：1983.2