6,6-pentamethylenebenzofulvene | 101111-41-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 6,6-pentamethylenebenzofulvene
• 英文别名: 1‐cyclohexylidene‐1H‐indene；1-Cyclohexyliden-inden；1-Cyclohexylideneindene；1-cyclohexylideneindene
• CAS: 101111-41-5
• 化学式: C₁₅H₁₆
• 分子量: 196.292
• InChiKey: FRFDLVUVIWJVCU-UHFFFAOYSA-N

物化性质

• 沸点：
  127-130 °C(Press: 1 Torr)
• 密度：
  1.083±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  2-噻吩基锂 、 6,6-pentamethylenebenzofulvene 以 乙醚 为溶剂， 反应 24.0h， 以24%的产率得到2‐[1‐(3H‐inden‐1‐yl)cyclohexyl]thiophene
  参考文献：
  名称：

  使用基于TiCl3 /半三明治配体的催化剂优化乙烯三聚

  摘要：

  使用三个钛基配合物[η乙烯的三聚反应5 -C 9 ħ 6 C（R）噻吩基]的TiCl 3与各种类型的桥（R = 环-C 5 H ^ 10（C1），环-C 4 H ^ 8（C2）和（CH 3）2（C3））已成功优化和比较。首先，三种苯并富勒烯前体C 9 H 6合成。然后，通过前体与噻吩锂的反应获得相应的基于茚基的配体。最终的钛基催化剂表现出扭曲的四面体几何形状，这是Ti（IV）所期望的，其配体与半不稳定的行为相协调。根据各种分析证实了化合物的结构。研究了催化剂浓度，乙烯压力，反应温度和桥的性质作为影响噻吩基相对于金属中心的配位和取向的重要因素对1-己烯（1-C 6）生产率和选择性的影响。结果表明，庞大的桥基，如cyclo- C 5 H 10和环-C 4 H ^ 8是适合于乙烯三聚由于与钛硫原子的更密切的协调，尤其是在阳离子状态，和催化剂C2与环-C 4 H ^ 8桥表现出中度的生产率等于785公斤1-C

  DOI：

  10.1002/aoc.4666
• 作为产物：
  描述：

  环己酮 、 茚 在 四氢吡咯 作用下， 以 甲醇 为溶剂， 反应 12.0h， 生成 6,6-pentamethylenebenzofulvene
  参考文献：
  名称：

  钛基半夹心茂金属催化剂的实验和DFT研究及其在乙烯制备1-己烯中的应用

  摘要：

  不同类型的[Ind-C(R)-苯基]TiCl 3催化剂基于含茚基(Ind)配体的悬垂芳烃，带有各种类型的桥(R=环-C 5 H 10 (C1), (CH 3 ) 2 ( C2)、4- t Bu-环-C 5 H 9 (C3)和环-C 6 H 12(C4)) 已被合成，并用于在甲基铝氧烷 (MAO) 作为助催化剂存在下乙烯三聚生成 1-己烯。反应条件首先在 C2 催化剂情况下进行优化，其中在催化剂浓度、温度和乙烯压力为 1.5 时获得了最高的 1-己烯产物×分别为 10 -3 M、40 °C 和 8 bar。在此优化过程中和在特定反应条件下，还检测到从乙烯三聚到聚合的转换行为，这是不希望的反应。在优化条件下，合成的催化剂在 1-己烯产率和选择性方面表现出以下趋势：C1>C2>C3>C4。然后，为了阐明可能的反应机制并确认实验部分获得的活性趋势，采用了密度泛函理论 (DFT) 计算。在这条线上，

  DOI：

  10.1016/j.mcat.2021.111636

文献信息

• Highly selective trimerization of ethylene with half-sandwich cyclopentadienyl and indenyl titanium complexes bearing pendant thienyl group
  作者：Yanlu Zhang、Chen Wang、Tianzhi Wu、Haiyan、Ma. Jiling Huang

  DOI：10.1016/j.molcata.2014.02.010

  日期：2014.6

  A series of half-sandwich titanium complexes bearing thienyl group [Cp(Ind)-bridge-thienyl]TiCl3 (CS1-CS10) have been synthesized and show high selective ethylene trimerizaion to 1-hexene. The molecular structure of CS8 [Ind-C(cyclo-C5H10)-(5-Me-thienyl)]TiCl3 was confirmed by X-ray. No intramolecular coordination interaction between the sulfur atom on the thienyl group and the titanium center could be observed in the solid state of these complexes. After activated with MAO, the complexes can effectively catalyze ethylene trimerization. For [Cp-bridge-thienyl]TiCl3/MAO system, the best productivity is obtained at 30 degrees C; increasing the bulk of the substituent on the 5-position of the thienyl can improve the productivity for 1-hexene. CS6 [Cp-C(cyclo-C5H10)-(5-SiMe3-thienyl)]TiCl3 upon with MAO can make a productivity of 553 kg/(mol Ti-h) and 1-hexene selectivity of 86% at 30 degrees C, 0.5 MPa ethylene pressure. For [Ind-bridge-thienyl] TiCl3/MAO system, catalysts have more active and more tolerant of temperature comparing to corresponding Cp complexes. For example, CS8 can make the productivity of 697 kg/(mol Ti-h) and 1-hexene selectivity of 95% at 80 degrees C, 0.5 MPa ethylene. (C) 2014 Elsevier B.V. All rights reserved.
• Highly selective ethylene trimerization catalyzed by half-sandwich indenyl titanium complexes with pendant arene groups and MAO
  作者：Yanlu Zhang、Haiyan Ma、Jiling Huang

  DOI：10.1016/j.molcata.2013.03.005

  日期：2013.7

  A series of half-sandwich indenyl titanium complexes [Ind-(bridge)-Ar]TiCl3 (C1-C9) bearing pendant arene group on indenyl ring have been synthesized and used for the catalytic ethylene trimerization to 1-hexene in the presence of MAO. The molecular structures of complexes C3 [Ind-C(cydo-C5H10)-Ph]TiCl3 and C5 [Ind-C(cyclo-C5H10)-(p-MePh)]TiCl3 have been established by single-crystal X-ray diffraction study. No intramolecular coordination interaction between the arene moiety and the titanium center could be observed in the solid state of these complexes. At 0 degrees C and 0.8 MPa of ethylene pressure, upon activation with MAO, C3 possesses the highest activity of 1968 kg of 1-hexene/(mol-Tih) and the overall selectivity of 95.9% by mass for 1-hexene, and is also more active than the corresponding cyclopentadienyl analog [Cp-C(cyclo-C5H10)-Ph]TiCl3 (C10) under the identical conditions. The substituents of various steric and electronic effects on the pendant arene group and the bridge unit between the indenyl and this arene group exert great influence on the activity and selectivity of these indenyl titanium complexes for ethylene trimerization to 1-hexene. Similar to cyclopentadienyl analogs, upon activation with MAO the resultant indenyl catalytic systems also show great sensitivity to the temperature. With the increase of the reaction temperature, both the activity and selectivity of 1-hexene declined. (C) 2013 Elsevier B.V. All rights reserved.
• Tsytovich,N.E.; Pokrovskaya,E.S., Doklady Chemistry, 1960, vol. 134, p. 1163 - 1165
  作者：Tsytovich,N.E.、Pokrovskaya,E.S.

  DOI：——

  日期：——
• Experimental and DFT study on titanium-based half-sandwich metallocene catalysts and their application for production of 1-hexene from ethylene
  作者：Sajjad Gharajedaghi、Zahra Mohamadnia、Ebrahim Ahmadi、Mohamadreza Marefat、Gerard Pareras、Sílvia Simon、Albert Poater、Naeimeh Bahri-Laleh

  DOI：10.1016/j.mcat.2021.111636

  日期：2021.6

  8 bar, respectively. During this optimization and under specific reaction conditions, a switching behavior from ethylene trimerization to polymerization was also detected, as an undesired reaction. At the optimized conditions, synthesized catalysts showed the following trend toward both 1-hexene yield and selectivity: C1>C2>C3>C4. Then, to shed light on the possible reaction mechanisms and to confirm

  不同类型的[Ind-C(R)-苯基]TiCl 3催化剂基于含茚基(Ind)配体的悬垂芳烃，带有各种类型的桥(R=环-C 5 H 10 (C1), (CH 3 ) 2 ( C2)、4- t Bu-环-C 5 H 9 (C3)和环-C 6 H 12(C4)) 已被合成，并用于在甲基铝氧烷 (MAO) 作为助催化剂存在下乙烯三聚生成 1-己烯。反应条件首先在 C2 催化剂情况下进行优化，其中在催化剂浓度、温度和乙烯压力为 1.5 时获得了最高的 1-己烯产物×分别为 10 -3 M、40 °C 和 8 bar。在此优化过程中和在特定反应条件下，还检测到从乙烯三聚到聚合的转换行为，这是不希望的反应。在优化条件下，合成的催化剂在 1-己烯产率和选择性方面表现出以下趋势：C1>C2>C3>C4。然后，为了阐明可能的反应机制并确认实验部分获得的活性趋势，采用了密度泛函理论 (DFT) 计算。在这条线上，
• Optimization of ethylene trimerization using catalysts based on TiCl₃ /half-sandwich ligands
  作者：Leila Azimnavahsi、Zahra Mohamadnia

  DOI：10.1002/aoc.4666

  日期：2019.2

  The final titanium‐based catalysts display a distorted tetrahedral geometry, as expected for Ti(IV), with the ligand coordinated with a hemilabile behaviour. The structures of the compounds were confirmed on the basis of various analyses. The effect of catalyst concentration, ethylene pressure, reaction temperature and nature of the bridge as the significant factor affecting coordination and orientation

  使用三个钛基配合物[η乙烯的三聚反应5 -C 9 ħ 6 C（R）噻吩基]的TiCl 3与各种类型的桥（R = 环-C 5 H ^ 10（C1），环-C 4 H ^ 8（C2）和（CH 3）2（C3））已成功优化和比较。首先，三种苯并富勒烯前体C 9 H 6合成。然后，通过前体与噻吩锂的反应获得相应的基于茚基的配体。最终的钛基催化剂表现出扭曲的四面体几何形状，这是Ti（IV）所期望的，其配体与半不稳定的行为相协调。根据各种分析证实了化合物的结构。研究了催化剂浓度，乙烯压力，反应温度和桥的性质作为影响噻吩基相对于金属中心的配位和取向的重要因素对1-己烯（1-C 6）生产率和选择性的影响。结果表明，庞大的桥基，如cyclo- C 5 H 10和环-C 4 H ^ 8是适合于乙烯三聚由于与钛硫原子的更密切的协调，尤其是在阳离子状态，和催化剂C2与环-C 4 H ^ 8桥表现出中度的生产率等于785公斤1-C