2,2'-bis(2-indenyl)biphenyl | 152952-99-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,2'-bis(2-indenyl)biphenyl
• 英文别名: 2,2'-Bis(2-indenyl) biphenyl；2-[2-[2-(1H-inden-2-yl)phenyl]phenyl]-1H-indene
• CAS: 152952-99-3
• 化学式: C₃₀H₂₂
• 分子量: 382.505
• InChiKey: DGTWDUGCMACYFO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  2,2'-bis(2-indenyl)biphenyl 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Indenyl compounds for the polymerization of olefins

  摘要：

  式（1）的茚基化合物 其中： M是来自镧系元素或元素周期表第3、4、5或6族的过渡金属， Q是与M形成阴离子配体， k是Q基团的数量， R是一个桥接基团 Z和X是取代基，其中R至少包含一个与茚基在2位处形成键合的sp2杂化碳原子，但不包括二氯化钛（去氢萘并苯）.

  公开号：

  US06342622B1
• 作为产物：
  描述：

  2-溴化茚 在 bis-triphenylphosphine-palladium(II) chloride 、 potassium phosphate 、 三乙胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 53.5h， 生成 2,2'-bis(2-indenyl)biphenyl
  参考文献：
  名称：

  [EN] PROCESS FOR THE PREPARATION OF METALLOCENE COMPLEXES
  [FR] PROCÉDÉ POUR LA PRÉPARATION DE COMPLEXES MÉTALLOCÈNES

  摘要：

  该发明涉及一种包括以下步骤的过程：(a)在Pd催化剂双(三苯基膦)氯化钯(PPh3)2PdCl2)和碱的存在下，将2-茚硼酸(酯)与溴取代化合物反应，形成相应的桥联双(茚)配体。如果2-茚硼酸(酯)是2-茚硼酸的缩二醇酯，该发明的过程还可以包括以下步骤：在Pd催化剂和碱的存在下，将2-溴茚烯化合物与缩二醇硼烷反应，形成相应的2-茚基缩二醇硼烷化合物。通过这种方法，该发明提供了一种改进和简便的两步法制备桥联双(茚)配体的方法，特别是当使用Pd催化剂双(三苯基膦)氯化钯(PPh3)2PdCl2)时，具有商业吸引力。桥联双(茚)配体可用于制备金属环烯配合物，如2,2'-双(2-茚基)联苯锆二氯化物和1,2-双(2-茚基)苯锆二氯化物。这些金属环烯配合物可用于聚合反应，可选地在协同催化剂的存在下，用于一个或多个α-烯烃的聚合，特别是用于乙烯的聚合。

  公开号：

  WO2013091836A1

文献信息

• [EN] PROCESS FOR THE PREPARATION OF 2,2'-BIS-INDENYL BIPHENYL LIGANDS AND THEIR METALLOCENE COMPLEXES<br/>[FR] PROCÉDÉ DE PRÉPARATION DE LIGANDS 2,2'-BIS-INDÉNYL BIPHÉNYLE ET DE LEURS COMPLEXES MÉTALLOCÈNES
  申请人：SAUDI BASIC IND CORP

  公开号：WO2015024938A1

  公开（公告）日：2015-02-26

  The invention relates to a novel process for the preparation of 2, 2'- bis indenyl biphenyl Iigands of following formula (3): The invention also relates to metallocene complexes prepared using the novel process for the preparation of 2, 2-bis indenyl biphenyl Iigands. The invention also relates to novel intermediates used in the process for the preparation of 2, 2'-bis indenyl biphenyl Iigands.

  这项发明涉及一种用于制备以下式（3）的2,2'-双茚基联苯配体的新型工艺。该发明还涉及使用该新型工艺制备的茂金属配合物。该发明还涉及用于制备2,2'-双茚基联苯配体的新型中间体。
• [EN] PROCESS FOR THE PREPARATION OF METALLOCENE COMPLEXES<br/>[FR] PROCÉDÉ DE PRÉPARATION DE COMPLEXES MÉTALLOCÈNES
  申请人：SAUDI BASIC IND CORP SABIC

  公开号：WO2013091837A1

  公开（公告）日：2013-06-27

  The invention relates to a process comprising the step of reacting a 2-indenylpinacolyl borane compound with a bromosubstituted compound in the presence of a Pd catalyst and a base to form the corresponding bridged bis(indenyl) ligand. This process step is very efficient and leads to less (homocoupled) byproducts than other known processes. The process of the invention may further comprise the step of reacting a 2-bromo indene compound with pinacolborane in the presence of a Pd catalyst and a base, to form the corresponding 2-indenylpinacolylborane compound. With this, the invention provides an improved and easy two-step process to prepared bridged bis(indenyl)ligands. These bridged bis(indenyl)ligands may suitably be used in the preparation of metallocene complexes, such as 2,2'-bis(2-indenyl)biphenyl ZrCI2 and 1,2-bis(2-indenyl)benzene ZrCI2. These metallocene complexes may be used for the polymerization, optionally in the presence of a cocatalyst, of one or more a-olefins, preferably for the polymerization of ethylene. In a preferred embodiment, the Pd catalyst is preferably is(triphenylphosphin)palladium dichloride (PPh3)2PdCI2).

  该发明涉及一种工艺，包括将2-茚基丙二醇硼烷化合物与溴取代化合物在Pd催化剂和碱存在下反应，形成相应的桥联双(茚基)配体的步骤。这个工艺步骤非常高效，并且产生的副产物比其他已知的工艺少（同偶联）。该发明的工艺还可以包括将2-溴茚烯化合物与丙二醇硼烷在Pd催化剂和碱存在下反应的步骤，形成相应的2-茚基丙二醇硼烷化合物。因此，该发明提供了一种改进且简便的两步法制备桥联双(茚基)配体的工艺。这些桥联双(茚基)配体可以用于制备茂金属配合物，例如2,2'-双(2-茚基)联苯基锆二氯化物和1,2-双(2-茚基)苯基锆二氯化物。这些茂金属配合物可以用于聚合一种或多种α-烯烃，最好用于乙烯的聚合，可选地在协同催化剂的存在下。在一个首选实施例中，Pd催化剂首选是二氯化二(三苯基膦)钯(PPh3)2PdCl2。
• [EN] PROCESS FOR PRODUCING A BIPHENYL METALLOCENE COMPLEX<br/>[FR] PROCÉDÉ DE PRODUCTION D'UN COMPLEXE DE TYPE MÉTALLOCÈNE DE BIPHÉNYLE
  申请人：SABIC GLOBAL TECHNOLOGIES BV

  公开号：WO2021198509A1

  公开（公告）日：2021-10-07

  The invention relates to a process for preparing a boronic anhydride compound of formula (1), wherein, R1 - R4 are substituents as defined in the disclosure and 'B' stands for the element boron. The invention also describes a process of using the boronic anhydride of formula (1), to prepare a biphenyl metallocene complex of formula (4), wherein, R1 to R10, are substituents as defined in the disclosure; and wherein 'M' is a transition metal element, 'Q' is an halide anion, and 'P' is the valency of the transition metal element 'M' and indicates the number of halide anion present. In addition, the invention further describes a process of purifying the metallocene complex of formula (4) so as to render the overall metallocene complex synthesis process environmentally sustainable as well as cost effective by minimizing waste effluents.

  本发明涉及制备式（1）的硼酸酐化合物的过程，其中R1-R4是如本说明书所定义的取代基，'B'代表硼元素。本发明还描述了使用式（1）的硼酸酐来制备式（4）的联苯基金属茂配合物的过程，其中R1至R10是如本说明书所定义的取代基；'M'是过渡金属元素，'Q'是卤素阴离子，'P'是过渡金属元素'M'的价数，并表示存在的卤素阴离子的数量。此外，本发明还描述了纯化式（4）的茂配合物的过程，以使整个茂配合物合成过程在环境可持续和成本效益方面最大程度地减少废水排放。
• A Suzuki Coupling Based Route to 2,2‘-Bis(2-indenyl)biphenyl Derivatives
  作者：Edwin G. IJpeij、Felix H. Beijer、Henricus J. Arts、Claire Newton、Johannes G. de Vries、Gert-Jan M. Gruter

  DOI：10.1021/jo016040i

  日期：2002.1.1

  Because of the promising performance in olefin polymerization of 2,2'-bis(2-indenyldiyl)biphenyl zirconium dichloride, we developed a new and broadly applicable route to 2,2'-bis(2-indenyl)biphenyl derivatives. Reaction of the known 2,2'-diiodobiphenyl (26) with the new 2-indenyl boronic acid (23) did not result in the desired 2,2'-bis(2-indenyl)biphenyl (10); instead an isomer thereof, (spiro-1,1-(2,2'-biphenyl)-2-(2-indenyl)indane) (27), was obtained. It was found that compound 10 could be made via a palladium-catalyzed reaction of 2,2-biphenyldiboronic acid (31) with 2-bromoindene (21) under standard Suzuki reaction conditions. However, the yield of this reaction was low at low palladium catalyst loadings, due to a competitive hydrolysis reaction of 2,2-biphenyldiboronic acid (31). HTE techniques were used to find an economically viable protocol. Thus, use of the commercially available 1.0 molar solution of (n-BU)(4)NOH in methanol with cosolvent toluene led to precipitation of the pure product in a fast and clean reaction, using only 0.7 mol % (0.35 mol % per C-C) of the expensive palladium catalyst.
• Synthesis, structure, and properties of chiral titanium and zirconium complexes bearing biaryl strapped substituted cyclopentadienyl ligands
  作者：William W. Ellis、T. Keith Hollis、William Odenkirk、John Whelan、Robert Ostrander、Arnold L. Rheingold、B. Bosnich

  DOI：10.1021/om00035a026

  日期：1993.11

  The synthesis and characterization of 2,2'-bis(2-tetrahydroindenyl)biaryl metallocenes of titanium and zirconium which alleviate many of the stereochemical problems associated with previous ligand systems are described. Such systems give only a single chiral isomer of the complex, the biaryl link determines the chirality of the complex, and the tetrahydroindenyl ligands project their C2 chirality directly to the site of reaction. The reaction of the di-Grignard of o-bis(chloromethyl)benzene with the 2,2'-dimethyl esters of biphenyl, 6,6'-dimethylbiphenyl, and binaphthyl gave the corresponding bis(carbinols) in good yields. Acid catalyzed dehydrations of these diols gave the bis(2-indene) compounds in high yield. Both the racemic and the homochiral forms of the bis(2-indene) of the 6,6'-dimethylbiphenyl compound were prepared. Reaction of the dilithio anions of these indene compounds with TiCl3 and ZrCl4 gave the corresponding bis(indenyl) complexes which are sensitive to protic media and decomposed, in some cases rapidly, to the indene ligands. The protic sensitivity has been studied. The in situ prepared bis(2-indenyl) complexes are readily reduced with H-2 and Adam's catalyst to the tetrahydroindenyl complexes. The Ti(IV) and Zr(IV) tetrahydroindenyl complexes are stable in protic media. The yields of the complexes are generally good. X-ray diffraction structures for a bis(tetrahydroindenyl).0.5(hexane) and a bis(indenyl)metal complex (Ti(IV)) have been determined and confirm the expected structures.