4-bromo-7-methoxy-2-methylindene | 1379658-30-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 4-bromo-7-methoxy-2-methylindene
• 英文别名: 7-bromo-4-methoxy-2-methyl-1H-indene；7-bromo-4-methoxy-2-methylindene
• CAS: 1379658-30-6
• 化学式: C₁₁H₁₁BrO
• 分子量: 239.112
• InChiKey: UMJYPVLHXOHEPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-bromo-7-methoxy-2-methylindene 在 四(三苯基膦)钯 、 正丁基锂 作用下， 以 1,4-二氧六环 、 乙醇 、 正己烷 、 水 、 甲苯 为溶剂， 反应 98.0h， 生成 bis(4-phenyl-7-methoxy-2-methylindenyl)dimethylsilane
  参考文献：
  名称：

  丙烯的高度等选择性聚合的基于超刚性茚基的Ha茂配合物：采用各种立体要求较高的4-芳基取代基的可调聚合性能

  摘要：

  Two novel silyl-bridged C-2-symmetric (2-methyl-4-aryl-7-methoxy) substituted bisindenyl based ansa-hafnocene complexes of varied steric demand (I, 4-phenyl; II, 4-[(3',5'-methyl)-phenyl]) were synthesized and examined in the coordinative polymerization of propene. Both complexes enable a comparative study with the state of the art homogeneous metallocene catalyst (III, 4-[(3',S'-tert-butyl)-phenyl]) for high melting ultrahigh molecular weight isotactic polypropylene. All three activated complexes exhibit extremely concise stereoregularity along with high molecular weights and high melting transitions at low to moderate polymerization temperatures. Increased sterical encumbrance of the 4-aryl substituent prevents the process of chain release reactions more effectively, especially due to enhanced reduction of beta-methyl elimination. Accordingly, end group analysis disclosed the highest selectivity toward allylic chain ends as a result of beta-methyl elimination with the less sterically encumbered complex I. Examination of the catalytic activity of I III disclosed considerable impact of the varied 4-aryl substituents on the maximum productivity with respect to the applied polymerization conditions considering the combined influence of activation, monomer diffusion rate, catalyst deactivation, and rate of chain growth.

  DOI：

  10.1021/acs.organomet.6b00814
• 作为产物：
  描述：

  4-bromo-7-hydroxy-2-methylindanone 在 lithium aluminium tetrahydride 、 sodium ethanolate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 17.0h， 生成 4-bromo-7-methoxy-2-methylindene
  参考文献：
  名称：

  用于丙烯的异丁二烯和区域特异性聚合的超硬金属茂：寻找完美的聚丙烯螺旋

  摘要：

  完美的聚丙烯：提出了一种通用的合成路线，该路线可生成2、4和7个取代的双茚基茂金属（Zr，Hf），即使在高温下也能提供刚性的，因此高度立体和区域选择性的聚合催化剂。尤其是，f茂能够生产具有极高的熔融转变温度的全同立构聚丙烯，所述熔融转变温度超过170℃，且分子量超过5000000g mol -1。

  DOI：

  10.1002/chem.201103547

文献信息

• Multisubstituted <i>C</i>₂-symmetric <i>ansa</i>-metallocenes bearing nitrogen heterocycles: influence of substituents on catalytic properties in propylene polymerization at higher temperatures
  作者：Pavel S. Kulyabin、Vyatcheslav V. Izmer、Georgy P. Goryunov、Mikhail I. Sharikov、Dmitry S. Kononovich、Dmitry V. Uborsky、Jo Ann M. Canich、Alexander Z. Voskoboynikov

  DOI：10.1039/d1dt00645b

  日期：——

  2′-dibromobiaryls with 4-aminoindenes, which were synthesized via Buchwald–Hartwig reaction or electrophilic amination of 4-indenyl Grignard reagents with trimethylsilylmethyl azide. By a number of examples, the anion-promoted rac-to-meso isomerization method was shown to work reliably well for preparation of rac-ZrMe2-complexes. Certain zirconocenes among the 21 tested in propylene polymerization at

  在这项工作中，我们系统地研究了取代基修饰对基于异特异锆茂催化剂的Me 2 Si（2-Alk-4-（N -carbazolyl）Ind）ZrX 2（X = Cl，Me）性能的影响。 ，其中前体被证明特别适用于高温丙烯聚合工艺。为了获得所需的锆茂，我们开发了一种新的合成途径，即通过Pd催化2，2'-二溴联芳基与4-氨基茚的环化反应，生成4-（N-咔唑基）茚，这是通过Buchwald-Hartwig反应或亲电法合成的用三甲基甲硅烷基甲基叠氮化物将4-茚基格氏试剂胺化。通过许多例子，阴离子促进了外消旋-到-内消旋异构化方法被证明工作良好可靠制备的外消旋-ZrMe 2个-complexes。在MAO或硼酸盐活化下于70和100°C的丙烯聚合中测试的21种茂金属中，某些锆茂在分子量能力，区域选择性或立体选择性方面优于母体催化剂。
• Bridged Metallocene Catalysts
  申请人：Borealis AG

  公开号：EP2532687A3

  公开（公告）日：2013-04-10

  A catalyst comprising a complex of formula (I) wherein M is zirconium or hafnium; each X is a sigma ligand; L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom, C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl; each R2 is independently a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms from groups 14-16; each R5 is independently hydrogen or an aliphatic C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16; each R6 is independently hydrogen or an aliphatic C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16; or an R5 and R6 group on adjacent carbon atoms can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by a group R4; each R7 is independently an aliphatic C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 with at least 2 non-H atoms; each Ar group is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more groups R1; each R1 is a C1-20 hydrocarbyl group or two R1 groups on adjacent carbon atoms taken together can form a fused 5 or 6 membered non aromatic ring with the Ar group, said ring being itself optionally substituted with one or more groups R4; each R4 is a C1-20 hydrocarbyl group; and (ii) a cocatalyst comprising a compound of a group 13 metal, e.g. boron.

  一种催化剂，包括符号（I）的配合物，其中M为锆或铪；每个X为σ配体；L为从-R'2C-、-R'2C-CR'2-、-R'2Si-、-R'2Si-SiR'2-、-R'2Ge-中选择的二价桥，其中每个R'独立地为氢原子、C1-C20-烃基、三（C1-C20-烷基）硅基、C6-C20-芳基、C7-C20-芳基烷基或C7-C20-烷基芳基；每个R2独立地为一个C1-C20烃基基团，可选地含有来自第14-16族的一个或多个杂原子；每个R5独立地为氢或一个脂肪族C1-20烃基基团，可选地含有来自第14-16族的一个或多个杂原子；每个R6独立地为氢或一个脂肪族C1-20烃基基团，可选地含有来自第14-16族的一个或多个杂原子；或相邻碳原子上的一个R5和R6基团可以结合形成一个5成员饱和碳环，该碳环可选地由一个R4基团取代；每个R7独立地为一个脂肪族C1-20烃基基团，可选地含有来自第14-16族的一个或多个杂原子，至少有2个非氢原子；每个Ar基团独立地为一个最多含有20个碳原子的芳基或杂芳基基团，可选地由一个或多个R1基团取代；每个R1为一个C1-20烃基基团，或相邻碳原子上的两个R1基团可以结合形成一个融合的非芳香5或6成员环，与Ar基团一起，所述环本身可选地由一个或多个R4基团取代；每个R4为一个C1-20烃基基团；和（ii）包括第13族金属化合物的共催化剂，例如硼。
• US9598517B2
  申请人：——

  公开号：US9598517B2

  公开（公告）日：2017-03-21
• Ultra-Rigid Metallocenes for Highly Iso- and Regiospecific Polymerization of Propene: The Search for the Perfect Polypropylene Helix
  作者：Alexander Schöbel、Eberhardt Herdtweck、Matthew Parkinson、Bernhard Rieger

  DOI：10.1002/chem.201103547

  日期：2012.4.2

  Perfect polypropylene: A versatile synthesis route leading to 2‐, 4‐, and 7‐ substituted bisindenyl metallocenes (Zr, Hf) affording rigid and thus highly stereo‐ and regioselective polymerization catalysts, even at elevated temperatures, is presented. In particular, the hafnocene is able to produce isotactic polypropylene with extremely high melting transitions, exceeding 170 °C with molecular weights

  完美的聚丙烯：提出了一种通用的合成路线，该路线可生成2、4和7个取代的双茚基茂金属（Zr，Hf），即使在高温下也能提供刚性的，因此高度立体和区域选择性的聚合催化剂。尤其是，f茂能够生产具有极高的熔融转变温度的全同立构聚丙烯，所述熔融转变温度超过170℃，且分子量超过5000000g mol -1。
• Ultrarigid Indenyl-based Hafnocene Complexes for the Highly Isoselective Polymerization of Propene: Tunable Polymerization Performance Adopting Various Sterically Demanding 4-Aryl Substituents
  作者：Martin R. Machat、Dominik Lanzinger、Alexander Pöthig、Bernhard Rieger

  DOI：10.1021/acs.organomet.6b00814

  日期：2017.1.23

  Two novel silyl-bridged C-2-symmetric (2-methyl-4-aryl-7-methoxy) substituted bisindenyl based ansa-hafnocene complexes of varied steric demand (I, 4-phenyl; II, 4-[(3',5'-methyl)-phenyl]) were synthesized and examined in the coordinative polymerization of propene. Both complexes enable a comparative study with the state of the art homogeneous metallocene catalyst (III, 4-[(3',S'-tert-butyl)-phenyl]) for high melting ultrahigh molecular weight isotactic polypropylene. All three activated complexes exhibit extremely concise stereoregularity along with high molecular weights and high melting transitions at low to moderate polymerization temperatures. Increased sterical encumbrance of the 4-aryl substituent prevents the process of chain release reactions more effectively, especially due to enhanced reduction of beta-methyl elimination. Accordingly, end group analysis disclosed the highest selectivity toward allylic chain ends as a result of beta-methyl elimination with the less sterically encumbered complex I. Examination of the catalytic activity of I III disclosed considerable impact of the varied 4-aryl substituents on the maximum productivity with respect to the applied polymerization conditions considering the combined influence of activation, monomer diffusion rate, catalyst deactivation, and rate of chain growth.