1,1,4,4-tetramethyl-2,2,3,3-tetrahydrobenzo[b]fluorene | 77308-47-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1,1,4,4-tetramethyl-2,2,3,3-tetrahydrobenzo[b]fluorene
• 英文别名: 6,6,9,9-Tetramethyl-7,8,9,11-tetrahydro-6H-benzo[b]fluorene；6,6,9,9-tetramethyl-8,11-dihydro-7H-benzo[b]fluorene
• CAS: 77308-47-5
• 化学式: C₂₁H₂₄
• 分子量: 276.422
• InChiKey: ZWUALWBJXYMBEQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  1,1,4,4-tetramethyl-2,2,3,3-tetrahydrobenzo[b]fluorene 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 13.0h， 生成
  参考文献：
  名称：

  Structure-stereospecificity relationships of propylene polymerization using substituted ansa-silylene(fluorenyl)(amido) titanium complexes

  摘要：

  ansa-Fluorenylamidotitanium complexes bearing various substituents on the nitrogen and fluorene (2a-d) were synthesized. The structures of the complexes were characterized by H-1 and C-13 NMR, and X-ray crystal analyses were performed for complexes 2a, 2b and 2d. The coordination mode of the fluorenyl group to the metal center was changed from eta(3) to eta(1) when a bulky group was introduced on the nitrogen or 2,3-position of the fluorenyl ring. Syndiotactic-specificity of the catalyst for the propylene polymerization was reduced when bulky group was introduced on the nitrogen. Least-square fitting analysis of the steric pentad distributions revealed that the stereodefect was mainly formed by the chain migration without monomer insertion, which is accelerated by the eta(1)-coordination of the fluorenyl group. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.12.028
• 作为产物：
  描述：

  2,5-二甲基-2,5-己二醇 、 芴 在 三氯化铝 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到1,1,4,4-tetramethyl-2,2,3,3-tetrahydrobenzo[b]fluorene
  参考文献：
  名称：

  Guilhemat, Robert; Pereyre, Michel; Petraud, Michel, Bulletin de la Societe Chimique de France, 1980, vol. 2, # 7-8, p. 334 - 344

  摘要：

  DOI：

文献信息

• Sterically expanded CGC catalysts: substituent effects on ethylene and α-olefin polymerization
  作者：Jianfang Chai、Khalil A. Abboud、Stephen A. Miller

  DOI：10.1039/c3dt50163a

  日期：——

  Several analogues of the sterically expanded constrained geometry catalyst Me2Si(η1-C29H36)(η1-N-tBu)ZrCl2·OEt2 (2) were synthesized to assess the effect on branching and molecular weight for ethylene homopolymerization. Catalysts based on tetramethyltetrahydrobenzofluorene (TetH), ethylTetH, t-butylTetH, and octamethyloctahydrodibenzofluorenyl (OctH) bearing a diphenylsilyl bridge were prepared and characterized: Me2Si(η5-C21H22)(η1-N-tBu)ZrCl2 (3); Me2Si(η5-C23H26)(η1-N-tBu)ZrCl2 (4); and Me2Si(η5-C25H30)(η1-N-tBu)ZrCl2 (5); Me2Si(η5-C21H22)(η1-N-tBu)ZrMe2 (6); and Ph2Si(η5-C29H36)(η1-N-tBu)ZrCl2 (7). Complexes 4, 5, 6, and 7 were characterized by X-ray crystallography and displayed η5 hapticity to the carbon ring in each case, in contrast to 2. In comparison to 2, complexes 3, 4, 5, and 7 (in combination with methylaluminoxane = MAO) showed diminished branching, higher molecular weight, and higher polydispersity indices for obtained ethylene homopolymers. While 4/MAO produced the greatest molecular weight polymers, no branching was observed. Reactivity ratios were determined for the copolymerization of ethylene and 1-decene with 2/MAO. A value of rethylene = 14.9 and an exceedingly high value of r1-decene = 0.49 were found—in line with previous reports of this catalyst's unusual affinity for α-olefins.

  为了评估支化和分子量对乙烯均聚反应的影响，合成了立体扩张限制几何催化剂Me2Si(η1-C29H36)(η1-N-tBu)ZrCl2·OEt2 (2)的几种类似物。制备并表征了基于四甲基四氢二苯并芴（TetH）、乙基TetH、叔丁基TetH和八甲基八氢二苯并芴基（OctH）承载二苯硅桥的催化剂：Me2Si(η5-C21H22)(η1-N-tBu)ZrCl2 (3)；Me2Si(η5-C23H26)(η1-N-tBu)ZrCl2 (4)；以及Me2Si(η5-C25H30)(η1-N-tBu)ZrCl2 (5)；Me2Si(η5- )(η1-N-tBu)ZrMe2 (6)；和Ph2Si(η5- )(η1-N-tBu)ZrCl2 (7)。通过X射线晶体学对4、5、6和7进行表征，与2不同，这些配合物在每个碳环上都显示出η5的配位度。与2相比，配合物3、4、5和7（与甲基铝氧烷=MAO组合）得到的乙烯均聚物的支化程度降低，分子量更高，多分散性指数更高。尽管4/MAO生成了最高分子量的聚合物，但没有观察到分支。测定了乙烯和1-癸烯共聚反应中2/MAO的反应性比率。得到了rethylene = 14.9和极高的r1-癸烯 = 0.49的值，这与之前报道的该催化剂对α-烯烃的异常亲和力一致。
• GUILHEMAT R.; PERCYRE M.; PETRAUD M., BULL. SOC. CHIM. FRANCE, 1980, PART. 2, NO 7-8, 334-344
  作者：GUILHEMAT R.、 PERCYRE M.、 PETRAUD M.

  DOI：——

  日期：——