2,4,5,6-tetramethyl-4H-cyclopenta[b]thiophene | 1309589-90-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 2,4,5,6-tetramethyl-4H-cyclopenta[b]thiophene
• CAS: 1309589-90-9
• 化学式: C₁₁H₁₄S
• 分子量: 178.298
• InChiKey: DCKUNBSCDKTOMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,4,5,6-tetramethyl-4H-cyclopenta[b]thiophene 、 以 正己烷 为溶剂， 反应 24.0h， 以78%的产率得到(2,4,5,6-Me₄-4H-cyclopenta[b]thiophenyl)Sc(CH₂SiMe₃)₂THF
  参考文献：
  名称：

  杂环稠合的环戊二烯基Complex配合物的合成及乙烯与二环戊二烯的共聚催化

  摘要：

  杂环稠合的环戊二烯基scan双（烷基）配合物L 1 – 4 Sc（CH 2 SiMe 3）2 THF（（5-Me-1-Ph-环戊[ b ]吡咯-4-基）Sc（CH 2 SiMe 3）2 THF（1），（2,5-Me 2 -3-Ph-6 H-环戊[ b ]硫代苯基）Sc（CH 2 SiMe 3）2 THF（2），（2,4,5,6-Me 4 -4 H-环戊[ b ]硫代苯基）Sc（CH 2 SiMe 3）通过烷烃消除反应容易地合成了2 THF（3），（2,3,4,5,6-Me 5 -4 H-环戊[ b ]硫代苯基）Sc（CH 2 SiMe 3）2 THF）（4））。的Sc（CH 2森达3）3（THF）2与杂环稠合的环戊二烯基配体HL 1 - 4以高收率。配合物1 - 4进行了表征1 H和13C NMR光谱学和X射线衍射分析为THF溶剂化单体，采用半夹心几何形状。在[Ph 3 C] [B（C 6

  DOI：

  10.1021/om500992v
• 作为产物：
  描述：

  2-甲基噻吩 在 polyphosphoric acid 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 2,4,5,6-tetramethyl-4H-cyclopenta[b]thiophene
  参考文献：
  名称：

  Preparation of half-titanocenes of thiophene-fused trimethylcyclopentadienyl ligands and their ethylene copolymerization reactivity

  摘要：

  Methylthiophene-fused or dimethylthiophene-fused trimethylcyclopentadienyltitanium trichloride complexes, (eta(5)-Me4RC7S) TiCl3 (R = Me or H), are prepared, from which a chloride ligand is replaced with 2,6-diisopropylphenoxy, di(tert-butyl) ketimide, or tri(tert-butyl) phosphinimide ligand to yield (eta(5)-Me4RC7S)TiXCl2 (11, R Me, X iPr(2)C(6)H(3)O-; 12, R = H, X = iPr(2)C(6)H(3)O-; 13, R Me, X tBu(2)C N-; 14, R = H, X = tBu(2)C N-; 15, R Me, X = tBu(3)P Ne; 16, R = H, X = tBu(3)P Ne). The molecular structures of 11, 14, and 16 are confirmed by X-ray crystallography. The Cp(centroid)-Ti-N angles of 11, 14, and 16 (119.83 degrees, 111.98 degrees, and 125.34 degrees, respectively) are significantly larger than the corresponding angle observed for the related thiophene-fused and tetrahydroquinaldine-linked cyclopentadienyl complex (1), [(eta(5)-(Me4C7S)-(2-MeC9H9N-kN)] TiMe2 (106.6 degrees). The phenoxy complexes 11 and 12 shownegligible activity, while the ketimido and phosphinimido complexes 13-16 exhibit good activities (5-20 x 10(6) g/molTi h) for ethylene/1-octene copolymerization. The ketimido-complexes 13 and 14 are able to incorporate a high amount of 1-octene (15-16 mol%), while the phosphinimido-complexes 15 and 16 are not as capable (8 mol % 1-octene) under the identical polymerization conditions. The catalytic performance of 13-16 is inferior to 1 in terms of activity and comonomer incorporation. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.03.014

文献信息

• Self-assisted stereospecific polymerization of unmasked polar 4-methylthio-1-butene
  作者：Yunjie Chai、Chunji Wu、Dongtao Liu、Mingtao Run、Dongmei Cui

  DOI：10.1007/s11426-018-9438-7

  日期：2019.6

  showed extremely low activity and no selectivity for 1-hexene polymerization. Surprisingly, highly stereo-selective coordination polymerization of unprotected polar 4-methylthio-1-butene has been achieved in high activity for the first time under the same polymerization conditions. High-molecular-weight (Mn=110×103) and perfectly syn-diotactic (rrrr>99%) poly(4-methylthio-1-butene) (P(MTB)) was afforded

  极性烯烃的立体定向聚合一直是一个有吸引力的但具有挑战性的项目，因为单体的路易斯碱性极性基团通常对催化剂的路易斯酸性金属中心有毒。在这方面的贡献，噻吩融合环戊二烯基复合物钪1 - 3成功地合成。与烷基铝和有机硼酸盐结合使用时，这些络合物显示出极低的活性，并且对1-己烯聚合反应没有选择性。令人惊讶地，在相同的聚合条件下，首次以高活性实现了未保护的极性4-甲硫基-1-丁烯的高度立体选择性配位聚合。高分子量（M n = 110×10 3）和完全间同立构的（rrrr > 99％）聚（4-甲硫基-1-丁烯）（P（MTB））。因此提出了甲硫基辅助机制，即未掩盖的甲硫基与乙烯基一起通过σ-π螯合到活性active中心促进了聚合反应。此外，通过P（MTB）的氧化也容易制备甲基磺酰基官能化的间同立构聚（1-丁烯）。这些结果为合成功能化的立构规整聚烯烃提供了一条新途径。
• Preparation of half-titanocenes of thiophene-fused trimethylcyclopentadienyl ligands and their ethylene copolymerization reactivity
  作者：Eun Seok Park、Ji Hae Park、Hoseop Yun、Bun Yeoul Lee

  DOI：10.1016/j.jorganchem.2011.03.014

  日期：2011.6

  Methylthiophene-fused or dimethylthiophene-fused trimethylcyclopentadienyltitanium trichloride complexes, (eta(5)-Me4RC7S) TiCl3 (R = Me or H), are prepared, from which a chloride ligand is replaced with 2,6-diisopropylphenoxy, di(tert-butyl) ketimide, or tri(tert-butyl) phosphinimide ligand to yield (eta(5)-Me4RC7S)TiXCl2 (11, R Me, X iPr(2)C(6)H(3)O-; 12, R = H, X = iPr(2)C(6)H(3)O-; 13, R Me, X tBu(2)C N-; 14, R = H, X = tBu(2)C N-; 15, R Me, X = tBu(3)P Ne; 16, R = H, X = tBu(3)P Ne). The molecular structures of 11, 14, and 16 are confirmed by X-ray crystallography. The Cp(centroid)-Ti-N angles of 11, 14, and 16 (119.83 degrees, 111.98 degrees, and 125.34 degrees, respectively) are significantly larger than the corresponding angle observed for the related thiophene-fused and tetrahydroquinaldine-linked cyclopentadienyl complex (1), [(eta(5)-(Me4C7S)-(2-MeC9H9N-kN)] TiMe2 (106.6 degrees). The phenoxy complexes 11 and 12 shownegligible activity, while the ketimido and phosphinimido complexes 13-16 exhibit good activities (5-20 x 10(6) g/molTi h) for ethylene/1-octene copolymerization. The ketimido-complexes 13 and 14 are able to incorporate a high amount of 1-octene (15-16 mol%), while the phosphinimido-complexes 15 and 16 are not as capable (8 mol % 1-octene) under the identical polymerization conditions. The catalytic performance of 13-16 is inferior to 1 in terms of activity and comonomer incorporation. (C) 2011 Elsevier B.V. All rights reserved.
• Synthesis of Heterocyclic-Fused Cyclopentadienyl Scandium Complexes and the Catalysis for Copolymerization of Ethylene and Dicyclopentadiene
  作者：Runhai Chen、Changguang Yao、Meiyan Wang、Hongyan Xie、Chunji Wu、Dongmei Cui

  DOI：10.1021/om500992v

  日期：2015.1.26

  adopting a half-sandwich geometry. Upon activation of [Ph3C][B(C6F5)4]/AliBu3, these half-sandwich scandium complexes displayed various activities toward the copolymerization of ethylene (E) and dicyclopentadiene (DCPD). Complex 1, supported by the phenyl-substituted pyrrole-fused cyclopentadienyl ligand, showed a slightly higher activity than the phenyl-substituted thiophene-fused cyclopentadienyl complex

  杂环稠合的环戊二烯基scan双（烷基）配合物L 1 – 4 Sc（CH 2 SiMe 3）2 THF（（5-Me-1-Ph-环戊[ b ]吡咯-4-基）Sc（CH 2 SiMe 3）2 THF（1），（2,5-Me 2 -3-Ph-6 H-环戊[ b ]硫代苯基）Sc（CH 2 SiMe 3）2 THF（2），（2,4,5,6-Me 4 -4 H-环戊[ b ]硫代苯基）Sc（CH 2 SiMe 3）通过烷烃消除反应容易地合成了2 THF（3），（2,3,4,5,6-Me 5 -4 H-环戊[ b ]硫代苯基）Sc（CH 2 SiMe 3）2 THF）（4））。的Sc（CH 2森达3）3（THF）2与杂环稠合的环戊二烯基配体HL 1 - 4以高收率。配合物1 - 4进行了表征1 H和13C NMR光谱学和X射线衍射分析为THF溶剂化单体，采用半夹心几何形状。在[Ph 3 C] [B（C 6