9-tert-butyldimethylsilylfluorene | 147743-09-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-tert-butyldimethylsilylfluorene
• 英文别名: 9-fluorenyl-tert-butyldimethylsilane；9-t-Butyldimethylsilylfluorene；tert-butyl-(9H-fluoren-9-yl)-dimethylsilane
• CAS: 147743-09-7
• 化学式: C₁₉H₂₄Si
• 分子量: 280.485
• InChiKey: JYWZNGJIPRIIKK-UHFFFAOYSA-N

物化性质

• 沸点：
  365.6±31.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.85
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  9-tert-butyldimethylsilylfluorene 在 9-benzylfluorene cesium salt 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Carbon acidity. 77. Ion pair carbon acidities of some silanes in tetrahydrofuran

  摘要：

  The relative solvent-separated ion pair (SSIP) lithium acidity (PK(Li)/THF) and contact ion pair (CIP) cesium acidity (pK(Cs/THF)) were obtained for 9-fluorenyltrimethylsilane (1) (21.3, 21.6, respectively) and 9-fluorenyl-tert-butyldimethylsilane (2) (20.3, 20.6, respectively) in THF. Values for pK(Cs/THF) were determined at 25-degrees-C for (p-biphenylylmethyl)-tert-butyldimethylsilane (3), 35.4, benzyltrimethylsilane (4), 37.5, alpha,alpha-bis(trimethylsilyl)toluene (5), 34.1, 2-(trimethylsilyl)-1,3-dithiane (6), 33.5, (trimethylsilyl)acetonitrile (7), 28.8, and tris(trimethylsilyl)methane (8), 36.8. Some thermodynamic parameters were determined by measurements at other temperatures, and some ionic acidities (pK(FI)) were determined by conductivity studies. Carbanion stabilization by these silyl substituents varies from about 1 to over 3 pK units in different systems. 9,9-Bis(trimethylsilyl)fluorene (9) was found to undergo silyl transfer on treatment with various carbanions, but this reaction is slower than proton transfer.

  DOI：

  10.1021/jo00059a031
• 作为产物：
  描述：

  9-lithio-9-(tert-butyldimethylsilyl)fluorene 在 苯并[a]蒽 作用下， 以 四氢呋喃 为溶剂， 生成 9-tert-butyldimethylsilylfluorene
  参考文献：
  名称：

  Carbon acidity. 77. Ion pair carbon acidities of some silanes in tetrahydrofuran

  摘要：

  The relative solvent-separated ion pair (SSIP) lithium acidity (PK(Li)/THF) and contact ion pair (CIP) cesium acidity (pK(Cs/THF)) were obtained for 9-fluorenyltrimethylsilane (1) (21.3, 21.6, respectively) and 9-fluorenyl-tert-butyldimethylsilane (2) (20.3, 20.6, respectively) in THF. Values for pK(Cs/THF) were determined at 25-degrees-C for (p-biphenylylmethyl)-tert-butyldimethylsilane (3), 35.4, benzyltrimethylsilane (4), 37.5, alpha,alpha-bis(trimethylsilyl)toluene (5), 34.1, 2-(trimethylsilyl)-1,3-dithiane (6), 33.5, (trimethylsilyl)acetonitrile (7), 28.8, and tris(trimethylsilyl)methane (8), 36.8. Some thermodynamic parameters were determined by measurements at other temperatures, and some ionic acidities (pK(FI)) were determined by conductivity studies. Carbanion stabilization by these silyl substituents varies from about 1 to over 3 pK units in different systems. 9,9-Bis(trimethylsilyl)fluorene (9) was found to undergo silyl transfer on treatment with various carbanions, but this reaction is slower than proton transfer.

  DOI：

  10.1021/jo00059a031

文献信息

• ——
  作者：Jason S. Overby、Richard T. Woofter、Arnold L. Rheingold、Christopher D. Incarvito、Roger D. Sommer

  DOI：10.1023/a:1024221928841

  日期：——

  Three silyl-substituted fluorenes have been prepared by direct synthetic methods and structurally characterized by X-ray diffraction. The three silyl-substituted fluorenes studied were 9-trimethylsilylfluorene (1), 9-(tert-butyldimethyl) silylfluorene (2), and 2,7-di-tert- butyl-9- trimethylsilylfluorene (3). Complex 1 is orthorhombic, P2(1)2(1)2(1), a = 6.2681(14) Angstrom, b = 14.329(3) Angstrom, c = 15.231(4) Angstrom, Z = 4. Complex 2 is monoclinic, P2(1)/c, a = 12.1953(10) Angstrom, b = 6.9977( 6) Angstrom, c = 19.6536(17) Angstrom, beta = 93.818(2) degrees, Z = 4. Complex 3 is monoclinic, P2(1)/c, a = 11.9954( 9) Angstrom, b = 9.8978( 7) Angstrom, c = 18.5464(13) Angstrom, beta = 92.456(2) degrees, Z = 4. The long carbon-silicon bonds effectively remove any significant intramolecular interactions as little distortion is exhibited around the sp(3)-carbon atom and the fluorenyl backbone demonstrates near planarity. The bulky silicon substituents also prevent intermolecular interactions, as only a few close contacts less than 4.0 Angstrom exist in all three solid state structures.