2,7-di-tert-butyl-9-(trimethylsilyl)fluorene | 136480-41-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,7-di-tert-butyl-9-(trimethylsilyl)fluorene
• 英文别名: (2,7-Di-tert-butyl-9H-fluoren-9-yl)(trimethyl)silane；(2,7-ditert-butyl-9H-fluoren-9-yl)-trimethylsilane
• CAS: 136480-41-6
• 化学式: C₂₄H₃₄Si
• 分子量: 350.619
• InChiKey: RKQNKMRTZYMJBS-UHFFFAOYSA-N

物化性质

• 沸点：
  409.5±34.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  2,7-di-tert-butyl-9-(trimethylsilyl)fluorene 在 正丁基锂 作用下， 以6.37 g (67.8%)的产率得到2,7-di(t-butyl)-9-trimethylsilyl-9-fluorenylmethyl benzyl ether
  参考文献：
  名称：

  Amino acid protecting groups

  摘要：

  这项发明涉及以下公式的化合物：其中X为O、CR.sub.7 R.sub.8、S或NR.sub.9，其中R.sub.7和R.sub.8独立地为氢或较低的烷基，R.sub.9为较低的烷基；n为0或1；R.sub.1和R.sub.2独立地为氢、较低的烷基、单器官硅基、双器官硅基、三器官硅基、卤素、芳基或硝基；R.sub.3为氢、较低的烷基、单器官硅基、双器官硅基、三器官硅基、卤素、9-芴基烷基、环烷基、芳基或芳基烷基；R.sub.4和R.sub.5独立地为氢、较低的烷基或芳基，或者R.sub.4和R.sub.5中的一个为9-芴基；R.sub.6为H或COZ，其中Z为氨基酸、肽残基或脱离基；并且有以下规定：当n为0且R.sub.3为氢时，R.sub.1和R.sub.2不是氢、卤素或硝基；当n为0且R.sub.3为较低的烷基时，R.sub.1和R.sub.2不是氢；当X为O或CR.sub.7 R.sub.8且R.sub.7和R.sub.8为H时，R.sub.1、R.sub.2、R.sub.3、R.sub.4、R.sub.5和R.sub.6不同时为H。本发明的化合物在肽合成中作为对反应基团的阻断或保护基团而有用。本发明还涉及一种在改变分子的部分而非受保护基团的反应中保护有机分子的反应基团的方法。

  公开号：

  US05101059A1
• 作为产物：
  描述：

  2,7-二叔丁基芴 在 正丁基锂 、 三甲基氯硅烷 作用下， 以10.43 g (82.7%)的产率得到2,7-di-tert-butyl-9-(trimethylsilyl)fluorene
  参考文献：
  名称：

  Amino acid protecting groups

  摘要：

  这项发明涉及以下公式的化合物：其中X为O、CR.sub.7 R.sub.8、S或NR.sub.9，其中R.sub.7和R.sub.8独立地为氢或较低的烷基，R.sub.9为较低的烷基；n为0或1；R.sub.1和R.sub.2独立地为氢、较低的烷基、单器官硅基、双器官硅基、三器官硅基、卤素、芳基或硝基；R.sub.3为氢、较低的烷基、单器官硅基、双器官硅基、三器官硅基、卤素、9-芴基烷基、环烷基、芳基或芳基烷基；R.sub.4和R.sub.5独立地为氢、较低的烷基或芳基，或者R.sub.4和R.sub.5中的一个为9-芴基；R.sub.6为H或COZ，其中Z为氨基酸、肽残基或脱离基；并且有以下规定：当n为0且R.sub.3为氢时，R.sub.1和R.sub.2不是氢、卤素或硝基；当n为0且R.sub.3为较低的烷基时，R.sub.1和R.sub.2不是氢；当X为O或CR.sub.7 R.sub.8且R.sub.7和R.sub.8为H时，R.sub.1、R.sub.2、R.sub.3、R.sub.4、R.sub.5和R.sub.6不同时为H。本发明的化合物在肽合成中作为对反应基团的阻断或保护基团而有用。本发明还涉及一种在改变分子的部分而非受保护基团的反应中保护有机分子的反应基团的方法。

  公开号：

  US05101059A1

文献信息

• Thermally Stable Half-Sandwich Benzhydryl Ln(II) (Ln = Sm, Yb) Complexes Supported by Sterically Demanding Carbazolyl and Fluorenyl Ligands
  作者：Alexander N. Selikhov、Andrey S. Shavyrin、Anton V. Cherkasov、Georgy K. Fukin、Alexander A. Trifonov

  DOI：10.1021/acs.organomet.9b00624

  日期：2019.12.23

  A series of new isolable and thermally stable half-sandwich Ln(II) benzhydryl complexes coordinated by the sterically demanding ligands tert-butylcarbazol-9-yl [tBu4Carb]Ln[(p-tBu-C6H4)2CH](L) (Ln = Sm, L = DME (4); Ln = Yb, L = DME (5); Ln = Yb, L = TMEDA (6)) and 2,7-di-tert-butyl-fluoren-9-trimethylsilylyl [2,7-tBu2-9-Me3Si-C13H6]Yb[(p-tBu-C6H4)2CH](DME) (7) were synthesized by the alkane elimination

  一系列新的可分离且热稳定的半三明治Ln（II）苯二甲酰配合物，由立体要求高的配体叔丁基咔唑-9-基[ t Bu 4 Carb] Ln [（p - t Bu-C 6 H 4）2配位CH]（L）（Ln = Sm，L = DME（4）; Ln = Yb，L = DME（5）; Ln = Yb，L = TMEDA（6））和2,7-二叔丁基-芴-9-基trimethylsilylyl [2,7-吨卜2 -9-ME 3的Si-C 13 H ^ 6 ]镱[（p -吨卜-C通过[（pt Bu-C 6 H 4）2 CH] 2 Ln（L n）（Ln = Sm，Yb）与t Bu的烷烃消除反应合成6 H 4）2 CH]（DME）（7）4 CarbH和2,7 - t Bu 2 -9-Me 3 Si-C 13 H 7。X射线分析表明，在4，5，和7的二苯甲基配位体配位到在η与金属离子3配位模式，而在6它是η 1分结合的。在抗磁二苯甲基配位体的配位类型5
• Ca‐Mediated Styrene Polymerization: Tacticity Control by Ligand Design
  作者：Dirk F.‐J. Piesik、Karin Häbe、Sjoerd Harder

  DOI：10.1002/ejic.200700802

  日期：2007.12

  for inversion at the chiral benzylic carbon atom [18.7(2)–19.2(2) kcal/mol]. Complex 4 does not initiate styrene polymerization, which underscores the importance of a free coordination site at calcium. Complexes 5–9 initiate styrene polymerization, and the syndiotacticity of the obtained polymers increases with the bulkiness of the substituents on the fluorenyl ligands. Syndiotacticities up to r = 95 %

  制备了具有修饰芴基配体的新型杂配苄基钙配合物，其中包括具有螯合二甲氨基取代基的配合物，[9-(2-Me2N-乙基)芴基][2-Me2N-α-Me3Si-苄基]Ca(4)，以及在芴基配体的 2 位和 7 位具有大量取代基的一系列配合物，如 tBu-、Ph(Me)2C-、Me(Ph)2C- 和 Me(4-tBuC6H4)2C-（配合物 5 到 9，分别）。4、[(2,7-tBu-9-Me3Si-芴基)(2-Me2N-苄基)Ca]2(5)和[2,7-Ph(Me)2C-9-Me3Si-芴基]的晶体结构[2-Me2N-α-Me3Si-苄基]Ca·THF (6) 表明芴基配体的修饰几乎不影响苄基配体的配位模式。此外，在溶液中，所有化合物都具有杂配性质，并且表明芴基修饰几乎不会影响手性苄基碳原子上的反转势垒[18.7(2)-19。2(2) 千卡/摩尔]。配合物 4 不会引发苯乙烯聚合，这强调了钙处自由配位点的重要性。配合物
• Sandwich and Half-Sandwich Ln(II) (Ln = Sm, Yb) Complexes with Bulky Fluorenyl Ligands. Competitive Abstraction of H or SiMe₃ from 2,7-<i>t</i>Bu₂-9-SiMe₃-Fluorene by an Amido Anion
  作者：Alexander N. Selikhov、Ivan V. Lapshin、Anton V. Cherkasov、Georgy K. Fukin、Alexander A. Trifonov

  DOI：10.1021/acs.organomet.1c00406

  日期：2021.9.13

  (5) could be synthesized in 80% yield when [(p-tBuC6H4)2 CH]2Sm(DME)2 was used as a precursor. The complex (2,7-tBu2C13H7)2Sm(THF)2 (6) was synthesized by the reaction of 2,7-tBu2C13H8 with [(Me3Si)2N]2Sm(THF)2 (2:1) in 65% yields. The crystal structures of complexes 1, 2a,b, 3, 5, and 6 were established by X-ray analyses.

  半夹心芴基酰氨基配合物[2,7-吨卜2 -9-森达3 Ç 13 ħ 6 ]的Yb [N（森达3）2 ]（DME）中的溶液通过反应合成[（ME 3 Si）的2 N] 2 Yb(THF) 2与2,7 - t Bu 2 -9-SiMe 3 C 13 H 7 (1:1 摩尔比)，产率为 83%。[(Me 3 Si) 2 N] 2 Sm(THF) 2的类似反应得到等摩尔量的半夹心配合物[2,7-t Bu 2 -9-SiMe 3 C 13 H 6 ]Sm[N(SiMe 3 ) 2 ](DME) ( 2a ) 和杂配体夹层 [2,7- t Bu 2 -9-SiMe 3 C 13 H 6 ]Sm [2,7- t Bu 2 C 13 H 7 ](DME) ( 2b )。杂配体夹心复合物 [2,7- t Bu 2 -9-SiMe 3 C 13 H 6 ]Sm[2,7- t Bu 2 -C 13H 7 ](THF)
• Aluminum Effects in the Syndiospecific Copolymerization of Styrene with Ethylene by Cationic Fluorenyl Scandium Alkyl Catalysts
  作者：Xiaofang Li、Xiaoying Wang、Xin Tong、Hongxia Zhang、Yuanyuan Chen、Ying Liu、Hui Liu、Xiaojie Wang、Masayoshi Nishiura、Huan He、Zhenguo Lin、Shaowen Zhang、Zhaomin Hou

  DOI：10.1021/om3011036

  日期：2013.3.11

  A series of half-sandwich fluorenyl (Flu') scandium dialkyl complexes Flu'Sc(CH2SiMe3)(2)(THF)(n) (1, Flu' = C13H9, n = 1; 2, Flu' = 2,7-(Bu2C13H7)-Bu-t, n = 1; 3, Flu' = 9-SiMe3C13H8, n = 1; 4, Flu' = 2,7-Bu-t(2)-9-SiMe3C13H6, n = 1; 5, Flu' = 9-CH2CH2NMe2C13H6, n = 0; 6, Flu' = 2,7-Bu-t(2)-9-CH2CH2NMe2C13H6, n = 0) have been synthesized and structurally characterized. In comparison with the well-known cyclopentadienyl-ligated scandium catalyst system [(C5Me4SiMe3)Sc-(CH2SiMe3)(2)(THF)]/[Ph3C][B(C6F5)(4)], the analogous combinations of the fluorenyl-ligated, THF-containing complexes 1-4 with [Ph3C] [B(C6F5)(4)] show relatively low activities, albeit with similar syndioselectivities for styrene polymerization and styrene-ethylene copolymerization. However, on treatment with 15 equiv of (AlBu3)-Bu-t, the 1-4/[Ph3C][B(C6F5)(4)] combinations show a dramatic increase in catalytic activity without changes in the stereoselectivity. In contrast, the combinations of complexes 5 and 6, which have an amino group attached to the fluorenyl ring and intramolecularly bonded to the metal center, exhibit very low activity, no matter whether or not All3u3 is present, affording syndiotactic polystyrenes with broad molecular weight distributions. The DFT calculations of the activation mechanism by using the representative catalysts suggest that Arl3u3 can capture the THF molecule from the catalyst precursors 1-4 at first,and then the new, THF-free cationic half-sandwich scandium active species [Flu'Sc(CH2SiMe3)][B(C6F5)(4)] with less steric hindrance around the metal center is generated in the presence of an activator such as [Ph3C][B(C6F5)(4)]. The DFT calculations on the syndioselectivity of styrene (co)polymerization catalyzed by [Flu'Sc(CH2SiMe3)][B(C6F5)(4)] have also been carried out, thus shedding new light on the mechanistic aspects of the (co)polymerization processes.
• ——
  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.