2,3,4,5,6-pentamethyl-4H-cyclopenta[b]thiophene | 1309589-89-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2,3,4,5,6-pentamethyl-4H-cyclopenta[b]thiophene
• CAS: 1309589-89-6
• 化学式: C₁₂H₁₆S
• 分子量: 192.325
• InChiKey: MEQRHSBLKFSVLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  三甲基氯硅烷 、 2,3,4,5,6-pentamethyl-4H-cyclopenta[b]thiophene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以95%的产率得到trimethyl(2,3,4,5,6-pentamethyl-6H-cyclopenta[b]thien-6-yl)silane
  参考文献：
  名称：

  [EN] METAL COMPLEX COMPRISING AMIDINE AND THIOPHENE FUSED CYCLOPENTADIENYL LIGANDS
  [FR] COMPLEXE MÉTALLIQUE COMPRENANT DES LIGANDS DE CYCLOPENTADIÉNYLE FUSIONNÉS PAR AMIDINE ET THIOPHÈNE

  摘要：

  一种化学配合物，其化学式为（1）TCyLMXp（1），其中M为4族金属，Z为阴离子配体，p为1至2的数字，最好为2，TCy为一种噻吩融合的环戊二烯基型配体，其化学式为（2），其中R1和R2分别选自氢、卤素、C1-C10烷基、C5-C10环烷基、未取代或C1-C10烷基或C1-C4二烷基氨基取代的C6-C10芳基，特别是C1-C4烷基取代的苯基和SiR3、OR、NR2、SR、PR2，其中R分别表示C1-C10烷基、C5-C10环烷基、未取代或C1-C10烷基或C1-C4二烷基氨基取代的C6-C10芳基，特别是C1-C4烷基取代的苯基或R1和R2与噻吩环的2个双键碳原子连接在一起形成未取代或C1-C4烷基取代的脂肪族C5-C6环烯基环，R3、R4和R5分别选自氢、C1-C4烷基、未取代或C1-C4烷基和/或卤素，特别是氯或氟取代的C6-C10芳基，特别是C1-C4烷基取代的苯基和SiR3、OR、NR2、SR、PR2，其中R分别表示C1-C10烷基、C5-C10环烷基、未取代或C1-C10烷基或C1-C4二烷基氨基取代的C6-C10芳基，特别是C1-C4烷基取代的苯基，L为一种含有酰胺基的配体，其化学式为（3），其中含有酰胺基的配体通过亚胺氮原子与金属M共价结合，Sub1为未取代或C1-C4烷基和/或卤素，特别是氯或氟取代的C6-C10芳基取代基，特别是苯基，Sub2为含有15族元素的取代基，通过该取代基与亚胺碳原子结合或Sub1和Sub2与亚胺基一起形成化学式（3a）的配体，其中含有酰胺基的配体（3a）通过亚胺氮原子N2与金属M共价结合，苯环与酰胺环融合的部分可能未取代或含有进一步的取代基R7，该取代基R7分别为指数“q”选自氢、C1-C4烷基和卤素，其中q为0至4的数字，最好为0至2，最好为0，Sub4为含有14族元素的脂肪族或芳香族环状或线性取代基，通过该取代基与氨基氮原子N1结合，最好Sub4为C6-C10芳香环，最好为苯基，未取代或由卤素（特别是Cl或F）和C1-C4烷基等取代基取代。

  公开号：

  WO2019132687A1
• 作为产物：
  描述：

  2,3-二甲基噻吩 在 polyphosphoric acid 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 2,3,4,5,6-pentamethyl-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

• 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
• 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。
• METAL COMPLEX COMPRISING AMIDINE AND THIOPHENE FUSED CYCLOPENTADIENYL LIGANDS
  申请人：Arlanxeo Netherlands B.V.

  公开号：EP3732183A1

  公开（公告）日：2020-11-04
• 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.
• [EN] METAL COMPLEX COMPRISING AMIDINE AND THIOPHENE FUSED CYCLOPENTADIENYL LIGANDS<br/>[FR] COMPLEXE MÉTALLIQUE COMPRENANT DES LIGANDS DE CYCLOPENTADIÉNYLE FUSIONNÉS PAR AMIDINE ET THIOPHÈNE
  申请人：ARLANXEO NETHERLANDS BV

  公开号：WO2019132687A1

  公开（公告）日：2019-07-04

  A metal complex of the formula (1) TCyLMXp (1), wherein M is a group 4 metal Z is an anionic ligand, p is number of 1 to 2, preferably 2, TCy is a thiophene fused cyclopentadienyl-type ligand of the formula (2) wherein R1 and R2 being individually selected from the group of hydrogen, halogen, C1-C10 alkyl, C5-C10 cycloalkyl, and an unsubstituted or C1-C10-alkyl or C1-C4-dialkyl amino substituted С6-С10 aryl, in particular C1-C4-alkyl substituted phenyl and SiR3, OR, NR2, SR, PR2, wherein R means individually C1-C10-alkyl, C5-С10-cycloalkyl, and an unsubstituted or C1-C10-alkyl or C1-C4-dialkyl amino substituted C6-C10-aryl, in particular C1-C4-alkyl substituted phenyl or R1 and R2 together with the 2 double bond carbon atoms of the thiophene ring they are connected to form an unsubstituted or C1-C4-alkyl substituted aliphatic C5-C6-cycloalkene ring, R3, R4 and R5 being individually selected from the group of hydrogen, C1-C4 alkyl, unsubstituted or C1-C4-alkyl and/or halogen, in particular chlorine or fluorine substituted C6-C10-aryl, in particular C1-C4-alkyl substituted phenyl, and SiR3, OR, NR2, SR, PR2, wherein R means individually C1-C10-alkyl, C5-C10-cycloalkyl, and an unsubstituted or C1-C10-alkyl or C1-C4-dialkyl amino substituted C6-C10-aryl, in particular C1-C4-alkyl substituted phenyl and, L is an amidinate ligand of the formula (3) wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is an unsubstituted or C1-C4-alkyl and/or halogen, in particular chlorine or fluorine substituted C6-C10-aromatic substituent, in particular phenyl and Sub2 is a substituent comprising a heteroatom of group 15, through which Sub2 is bonded to the imine carbon atom or Sub1 and Sub2 together with the imino group they are connected to form a ligand of formula (3a) wherein the amidine-containing ligand (3a) is covalently bonded to the metal M via the imine nitrogen atom N2, wherein the benzo ring fused to the amidine ring may be unsubstituted or contain further substituents R7, which are individually of the index "q" selected from the group of hydrogen, C1-C4-alkyl and halogen and whereby q is a number of 0 to 4, preferably 0 to 2, most preferably 0, Sub4 is an aliphatic or aromatic cyclic or linear substituent comprising a group 14 atom through which Sub4 is bonded to the amino nitrogen atom N1, preferably Sub4 is a C6-C10 aromatic ring, preferably phenyl which is unsubstituted or substituted by one or more substituents from the group selected from halogen, in particular Cl or F and C1-C4-alkyl.

  一种化学配合物，其化学式为（1）TCyLMXp（1），其中M为4族金属，Z为阴离子配体，p为1至2的数字，最好为2，TCy为一种噻吩融合的环戊二烯基型配体，其化学式为（2），其中R1和R2分别选自氢、卤素、C1-C10烷基、C5-C10环烷基、未取代或C1-C10烷基或C1-C4二烷基氨基取代的C6-C10芳基，特别是C1-C4烷基取代的苯基和SiR3、OR、NR2、SR、PR2，其中R分别表示C1-C10烷基、C5-C10环烷基、未取代或C1-C10烷基或C1-C4二烷基氨基取代的C6-C10芳基，特别是C1-C4烷基取代的苯基或R1和R2与噻吩环的2个双键碳原子连接在一起形成未取代或C1-C4烷基取代的脂肪族C5-C6环烯基环，R3、R4和R5分别选自氢、C1-C4烷基、未取代或C1-C4烷基和/或卤素，特别是氯或氟取代的C6-C10芳基，特别是C1-C4烷基取代的苯基和SiR3、OR、NR2、SR、PR2，其中R分别表示C1-C10烷基、C5-C10环烷基、未取代或C1-C10烷基或C1-C4二烷基氨基取代的C6-C10芳基，特别是C1-C4烷基取代的苯基，L为一种含有酰胺基的配体，其化学式为（3），其中含有酰胺基的配体通过亚胺氮原子与金属M共价结合，Sub1为未取代或C1-C4烷基和/或卤素，特别是氯或氟取代的C6-C10芳基取代基，特别是苯基，Sub2为含有15族元素的取代基，通过该取代基与亚胺碳原子结合或Sub1和Sub2与亚胺基一起形成化学式（3a）的配体，其中含有酰胺基的配体（3a）通过亚胺氮原子N2与金属M共价结合，苯环与酰胺环融合的部分可能未取代或含有进一步的取代基R7，该取代基R7分别为指数“q”选自氢、C1-C4烷基和卤素，其中q为0至4的数字，最好为0至2，最好为0，Sub4为含有14族元素的脂肪族或芳香族环状或线性取代基，通过该取代基与氨基氮原子N1结合，最好Sub4为C6-C10芳香环，最好为苯基，未取代或由卤素（特别是Cl或F）和C1-C4烷基等取代基取代。