1-(trimethylsilyl)indene | 27397-33-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 1-(trimethylsilyl)indene
• 英文别名: 3-(Trimethylsilyl)indene；3H-inden-1-yl(trimethyl)silane
• CAS: 27397-33-7
• 化学式: C₁₂H₁₆Si
• 分子量: 188.345
• InChiKey: WUSROTTWZIQGTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  三甲基氯硅烷 、 1-(trimethylsilyl)indene 在 正丁基锂 作用下， 以 正己烷 为溶剂， 以85%的产率得到1,3-bis(trimethylsilyl)indene
  参考文献：
  名称：

  Alkyl-substituted indenyl titanium precursors for syndiospecific ziegler-natta polymerization of styrene

  摘要：

  A variety of 1- and 3-substituted alkylindenes (R = H, Me, Et, tert-butyl, Me(3)Si) as well as 2-methylindene and 3-(methylthio)indene have been prepared in good yields. The substituted indenes were converted into trimethylsilyl derivatives via reactions of intermediate organolithium complexes with chlorotrimethylsilane. The corresponding titanium complexes, (R-Ind)TiCl3, were synthesized in excellent yield from reactions of the trimethylsilyl derivatives with TiCl4. The titanium complexes were evaluated as styrene polymerization catalysts in toluene solution when activated by methylaluminoxane. Activities increased in the order: Cp < H(4)Ind < Ind < 1-(Me)Ind < 2-(Me)Ind. A steep drop in activity was observed when R = Et, tert-butyl, and Me(3)Si, corresponding to an increase in the steric bulk of the substituent in the catalyst precursor. 1-(MeS)IndTiCl(3) was found to be ineffective as a styrene polymerization catalyst. Syndiospecificities of the titanium complexes were generally very good (65-98%).

  DOI：

  10.1016/s0022-328x(96)06153-0
• 作为产物：
  描述：

  三甲基氯硅烷 、 茚 在 正丁基锂 作用下， 生成 1-(trimethylsilyl)indene
  参考文献：
  名称：

  Alkyl-substituted indenyl titanium precursors for syndiospecific ziegler-natta polymerization of styrene

  摘要：

  A variety of 1- and 3-substituted alkylindenes (R = H, Me, Et, tert-butyl, Me(3)Si) as well as 2-methylindene and 3-(methylthio)indene have been prepared in good yields. The substituted indenes were converted into trimethylsilyl derivatives via reactions of intermediate organolithium complexes with chlorotrimethylsilane. The corresponding titanium complexes, (R-Ind)TiCl3, were synthesized in excellent yield from reactions of the trimethylsilyl derivatives with TiCl4. The titanium complexes were evaluated as styrene polymerization catalysts in toluene solution when activated by methylaluminoxane. Activities increased in the order: Cp < H(4)Ind < Ind < 1-(Me)Ind < 2-(Me)Ind. A steep drop in activity was observed when R = Et, tert-butyl, and Me(3)Si, corresponding to an increase in the steric bulk of the substituent in the catalyst precursor. 1-(MeS)IndTiCl(3) was found to be ineffective as a styrene polymerization catalyst. Syndiospecificities of the titanium complexes were generally very good (65-98%).

  DOI：

  10.1016/s0022-328x(96)06153-0

文献信息

• Synthesis and Reactivity of Cyclopentadienyl and Indenyl Ligands Bearing ω-Fluorinated Pendant Groups. Crystal Structure of (ortho-F-C₆H₄)-CPh₂-C₅H₄SiMe₃
  作者：A. Khvorost、D. Lemenovskii、N. Ustynyuk、K. Rufanov、J. Kipke

  DOI：10.1515/znb-2002-1104

  日期：2002.11.1

  A series of cyclopentadienes and indenes with ω-fluorinated pendant groups have been synthesised and their reactivity towards metallating agents n-BuLi, NaH, TlOEt, Me3SiCl, Me3SnCl, TiHal4, ZrX4 (X = Cl, NMe2) has been investigated. The crystal structure of 1-trimethylsilyl- 3-(diphenyl-ortho-fluorophenyl-methyl)-cyclopentadiene (3) was determined.

  已经合成了一系列带有 ω-氟化侧基的环戊二烯和茚，并研究了它们对金属化剂 n-BuLi、NaH、TlOEt、Me3SiCl、Me3SnCl、TiHal4、ZrX4（X = Cl、NMe2）的反应性。确定了1-三甲基甲硅烷基-3-(二苯基-邻-氟苯基-甲基)-环戊二烯(3)的晶体结构。
• Kinetic and stereochemical factors in the hydralumination of alkenes and the configurational stability of the resulting carbonaluminum bond
  作者：John J. Eisch、Kennetih C. Fichter

  DOI：10.1016/0022-328x(83)85040-2

  日期：1983.7

  case of the silylindene. The isomerization of the hydralumination adduct could occur either by carbonaluminum bond inversion or by dehydralumination. The former process took place readily in the absence of Lewis bases, but the latter process required elevated temperatures and protracted times. The stable cis-hydralumination adducts could be protodealuminated with retention of configuration at the CAl

  为了确定立体化学，区域化学以及结构对反应性的影响，用二异丁基铝氢化物对一系列环状烯烃进行水合铝化反应。观察到的反应性等级为：> 1，1-二甲基-3-三甲基甲硅烷基茚> 1-甲基ena> 1，1-二甲基茚> 1-苯基ac→1，1-二甲基-3-苯基茚。通过在供体溶剂中工作，证明了顺式-水合铝化是动力学控制的添加方式。3-取代-1,1-二甲基茚的反应性反映了极性效应，而1-取代的反应性则反应了空间效应。除硅烷基茚的情况外，水合铝化的区域化学通常由空间因素决定。水合铝酸盐加合物的异构化可能通过碳铝键反转或脱水铝化而发生。前一种方法很容易在没有路易斯碱的情况下进行，但是后一种方法需要高温和延长时间。稳定的顺式尽管烯基体系产生了大量的1,3-二氢ac烯，但β-水合铝化加合物仍可被原脱铝，并保留CAl键的构型。通过氘标记，1 H NMR和化学降解研究阐明了这些异常水解产物的性质。为了允许进行上述研究，明确地合成了完整的C
• Synthesis of silyl indenes by ruthenium-catalyzed aldehyde- and acylsilane-enabled C–H alkylation/cyclization
  作者：Tao Zhang、Cheng Zhang、Xiunan Lu、Chengxing Peng、Yawei Zhang、Xiong Zhu、Guofu Zhong、Jian Zhang

  DOI：10.1039/d3ob01699d

  日期：——

  A ruthenium-catalyzed C–H alkylation/cyclization sequence is presented to prepare silyl indenes with atom and step-economy. This domino reaction is triggered by acyl silane-directed C–H activation, and an aldehyde controlled the following enol cyclization/condensation other than β-H elimination. The protocol tolerates a broad substitution pattern, and the further synthetic elaboration of silyl indenes

  提出了一种钌催化的 C–H 烷基化/环化序列，以原子和步骤经济的方式制备甲硅烷基茚。这种多米诺骨牌反应是由酰基硅烷引导的 C-H 活化引发的，醛控制着随后的烯醇环化/缩合，而不是 β-H 消除。该方案允许广泛的取代模式，并且甲硅烷基茚的进一步合成精制允许获得各种有趣的茚和茚满酮衍生物。
• Synthesis and reactions of tetracarbonylmanganese complexes of benzoylsilanes
  作者：Richard C. Cambie、Linda Chua Mui Mui、Peter S. Rutledge、Paul D. Woodgate

  DOI：10.1016/0022-328x(94)87271-6

  日期：1994.1

  Reactions of benzoylsilane with benzylpentacarbonylmanganese (1) give ortho-eta(2)-manganese complexes in high yield. The derived aldehyde complex can then be formed by fluoride-catalysed desilylation of the acylsilane complex. Coupling reactions of the acylsilane complexes with alkenes or alkynes are reported.
• Alkyl-substituted indenyl titanium precursors for syndiospecific ziegler-natta polymerization of styrene
  作者：Thomas E. Ready、James C.W. Chien、Marvin D. Rausch

  DOI：10.1016/s0022-328x(96)06153-0

  日期：1996.7

  A variety of 1- and 3-substituted alkylindenes (R = H, Me, Et, tert-butyl, Me(3)Si) as well as 2-methylindene and 3-(methylthio)indene have been prepared in good yields. The substituted indenes were converted into trimethylsilyl derivatives via reactions of intermediate organolithium complexes with chlorotrimethylsilane. The corresponding titanium complexes, (R-Ind)TiCl3, were synthesized in excellent yield from reactions of the trimethylsilyl derivatives with TiCl4. The titanium complexes were evaluated as styrene polymerization catalysts in toluene solution when activated by methylaluminoxane. Activities increased in the order: Cp < H(4)Ind < Ind < 1-(Me)Ind < 2-(Me)Ind. A steep drop in activity was observed when R = Et, tert-butyl, and Me(3)Si, corresponding to an increase in the steric bulk of the substituent in the catalyst precursor. 1-(MeS)IndTiCl(3) was found to be ineffective as a styrene polymerization catalyst. Syndiospecificities of the titanium complexes were generally very good (65-98%).