1,4-bis(bromodimethylsilyl)benzene | 78704-51-5

• 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: 1,4-bis(bromodimethylsilyl)benzene
• 英文别名: bromo-[4-[bromo(dimethyl)silyl]phenyl]-dimethylsilane
• CAS: 78704-51-5
• 化学式: C₁₀H₁₆Br₂Si₂
• 分子量: 352.216
• InChiKey: TUQOJLURZOLENN-UHFFFAOYSA-N

物化性质

• 沸点：
  309.6±25.0 °C(Predicted)
• 密度：
  1.38±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,4-bis(bromodimethylsilyl)benzene 在 正丁基锂 作用下， 以 丙酮 为溶剂， 反应 5.0h， 生成 ({4-[Dimethyl-(2-oxo-vinyl)-silanyl]-phenyl}-dimethyl-silanyl)-ethenone
  参考文献：
  名称：

  Phenyldimethylsilyl-Substituted Ketenes and Bisketenes

  摘要：

  The phenyldimethylsilyl-substituted monoketene PhMe(2)SiCH=C=O (1) and bisketene (PhMe(2)SiC=C=O)(2) (3) have been prepared and compared to the corresponding Me(3)Si- and t-BuMe(2)Si-substituted species. The C-13, O-17, and Si-29 NMR spectra fit the pattern shown by other silylketenes and provide no evidence for transmission of a substituent effect of the Ph group through the silicon to the ketenyl group, as has been proposed for PhMe(2)Si-substituted radicals. The UV spectrum of 1 does show a longer lambda and greater epsilon than for t-BuMe(2)SiCH=C=O, and this may indicate some interaction of the phenyl group with the ketene chromophore, while the greater reactivity of 1 in hydration compared to t-BuMe(2)SiCH=C=O is ascribed to the inductive effect of the phenyl. The very similar ring-opening reactivity of the bis(phenyldimethylsilyl)cyclobutenedione (6) to form 3 compared to the bis(Me(3)Si) analogues also provides no evidence of a significant interaction of the phenyl with the ketene. A new type of stabilized 1,8-bisketene based on the arylbis(dimethylsilyl) grouping, namely, 1,4-bis(ketenyldimethylsilyl)benzene (12), has been prepared for the first time.

  DOI：

  10.1021/jo9605197
• 作为产物：
  描述：

  1,4-二(二甲基硅烷基)苯 在 eosin 、 二溴甲烷 作用下， 生成 1,4-bis(bromodimethylsilyl)benzene
  参考文献：
  名称：

  基于曙红 Y 的氢原子转移光催化剂实现多氢硅烷的逐步按需功能化

  摘要：

  有机硅烷对现代人类社会至关重要，在功能材料、有机合成、药物发现和生命科学等领域有着广泛的应用。然而，它们的制备远非微不足道，杂配取代硅试剂的按需合成是一项艰巨的挑战。通过直接氢原子转移 (HAT) 光催化从氢硅烷中产生甲硅烷基代表了氢硅烷活化的原子、步骤、氧化还原和催化剂最经济的途径。在这里，鉴于中性伊红 Y 的绿色特性（例如其丰富、低成本、无金属、吸收可见光和出色的选择性），我们表明将其用作直接 HAT 光催化剂可以实现逐步定制功能化多氢硅烷，获得完全取代的硅化合物。通过利用这一策略，我们实现了在活性 C-H 键存在下优选的 Si-H 键夺氢、氢硅烷的多样化功能化（例如，烷基化、乙烯基化、烯丙基化、芳基化、氘化、氧化和卤化），并且显着二氢硅烷和三氢硅烷的选择性单官能化。

  DOI：

  10.1038/s41557-023-01155-8

文献信息

• Polycylopentadienyls: Synthesis of arylsilylcyclopentadienyl compounds and their η5-complexes with tungsten
  作者：Herbert Plenio

  DOI：10.1016/0022-328x(92)83456-r

  日期：1992.2

  A general route to arylsilylcyclopentadienyl compounds starting from 1,4-C6H4Br2, 2,6-C5NH3Br2 and 1,3,5-C6H3Br3 is described. The aryl bromides were treated with Mg/ClSiMe2H to give the aryldimethylsilanes 1,4-C6H4(SiMe2H)2, 2,6-C5NH3(SiMe2H)2, and 1,3,5-C6H3(SiMe2H)3 which after reaction with Cl2 or Br2 yielded the aryldimethylsilyl halides 1,4-C6H4(SiMe2Br)2, 2,6-C5NH3 (SiMe2Br)2, 1,3,5-C6H3(SiMe2X)3 (X = Br or Cl) in excellent yields. The halide can be replaced by various cyclopentadienides to give aryldimethylsilylcyclopentadienes of the general type 1,4-C6H4 (SiMe2CP)2 and 1,3,5-C6H3(SiMe2CP)3 (Cp = C5H5 (8,11), C5H3(t-C4H9)2 (9,12), C5HMe4 (10,13)). Compounds C6H5(SiMe2(C5H5)), 1,4-C6H4(SiMe2(C5H5))2 (8) and 1,3,5-C6H3(SiMe2(C5H5))3 (11) were in turn treated with NaH, (MeCN)3W(CO)3, and MeI to give the eta-5-bound complexes C6H5 (SiMe2(C5H4)W(CO)3Me) (14), 1,4-C6H4(SiMe2(C5H4)W(CO)3Me)2 (15), 1,3,5-C6H3(SiMe2(C5H4)-W(CO)3Me)3 (16), which contain up to three half-sandwich units within one molecule.
• MATSUMOTO H.; SHONO K.; NAGAI Y., ORG. PREP. AND PROCED. INT., 1981, 13, NO 2, 118-123
  作者：MATSUMOTO H.、 SHONO K.、 NAGAI Y.

  DOI：——

  日期：——
• Phenyldimethylsilyl-Substituted Ketenes and Bisketenes
  作者：Ronghau Liu、Romeo M. Marra、Thomas T. Tidwell

  DOI：10.1021/jo9605197

  日期：1996.1.1

  The phenyldimethylsilyl-substituted monoketene PhMe(2)SiCH=C=O (1) and bisketene (PhMe(2)SiC=C=O)(2) (3) have been prepared and compared to the corresponding Me(3)Si- and t-BuMe(2)Si-substituted species. The C-13, O-17, and Si-29 NMR spectra fit the pattern shown by other silylketenes and provide no evidence for transmission of a substituent effect of the Ph group through the silicon to the ketenyl group, as has been proposed for PhMe(2)Si-substituted radicals. The UV spectrum of 1 does show a longer lambda and greater epsilon than for t-BuMe(2)SiCH=C=O, and this may indicate some interaction of the phenyl group with the ketene chromophore, while the greater reactivity of 1 in hydration compared to t-BuMe(2)SiCH=C=O is ascribed to the inductive effect of the phenyl. The very similar ring-opening reactivity of the bis(phenyldimethylsilyl)cyclobutenedione (6) to form 3 compared to the bis(Me(3)Si) analogues also provides no evidence of a significant interaction of the phenyl with the ketene. A new type of stabilized 1,8-bisketene based on the arylbis(dimethylsilyl) grouping, namely, 1,4-bis(ketenyldimethylsilyl)benzene (12), has been prepared for the first time.