4,5-dihydro-5-methyl-6H-cyclopentathiophen-6-one | 13196-30-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,5-dihydro-5-methyl-6H-cyclopentathiophen-6-one
• 英文别名: 5-methyl-4,5-dihydro-6H-cyclopenta[b]thiophen-6-one；5-methyl-4,5-dihydro-cyclopenta[b]thiophen-6-one；5-Methyl-4,5-dihydro-cyclopenta[b]thiophen-6-on；5-Methyl-4,5-dihydro-6H-cyclopenta[b]-thiophen-6-one；5-Methyl-4,5-dihydro-6H-cyclopentathiophen-6-on；5-Methyl-thiaindanon-(6)；5-methyl-4,5-dihydrocyclopenta[b]thiophen-6-one
• CAS: 13196-30-0
• 化学式: C₈H₈OS
• 分子量: 152.217
• InChiKey: GANSKXZKECOJHQ-UHFFFAOYSA-N

物化性质

• 熔点：
  137-140 °C
• 沸点：
  95.5 °C(Press: 2 Torr)
• 密度：
  1.1890 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  45.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,5-dihydro-5-methyl-6H-cyclopentathiophen-6-one 在 4-二甲氨基吡啶 、 氢氧化钾 、 lithium hydroxide 、 硼烷四氢呋喃络合物 、 碘苯二乙酸 、 zinc diacetate 、 potassium hydrogencarbonate 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 137.0h， 生成 (R,R)-7a-methyl-2-phenyl-7,7a-dihydro-3aH-thieno[3',2':4,5]cyclopenta[1,2-d][1,3]oxazole
  参考文献：
  名称：

  Thieno[3',2':4,5]cyclopenta[1,2-d][1,3]恶唑啉的非对映选择性合成——铜催化二乙基锌与烯酮不对称共轭加成的新配体

  摘要：

  采用模块化方法首次制备了几种具有刚性三环骨架的新配体。通过使用与环戊二烯[b]噻吩骨架稠合的恶唑啉部分引入了手性。研究了这些配体对铜催化的 Et2Zn 对映选择性加成到查耳酮的效率和立体化学影响，使用在环戊二烯部分被甲基取代的配体 (R,R)-16 实现了高达 79% 的对映体过量。计算和 ESI 质谱研究表明，这些新化合物表现为 Cu+ 的单齿配体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejoc.200400351
• 作为产物：
  描述：

  1-(2-噻吩基)-1-丙酮 在 硫酸 作用下， 以 盐酸 、 乙醇 为溶剂， 反应 6.0h， 生成 4,5-dihydro-5-methyl-6H-cyclopentathiophen-6-one
  参考文献：
  名称：

  Bridged Dithienylethylenes as Precursors of Small Bandgap Electrogenerated Conjugated Polymers

  摘要：

  Bridged dithienylethylenes (DTEs) bearing solubilizing alkyl chains at various positions (2-5) have been synthesized by McMurry dimerization of cyclopenta[b]thiophen-6-ones. In order to introduce alkyl substituents at different positions of the DTE molecule, the precursor ketones have been prepared by different strategies based on a combination of Mannich or Wittig-Horner reaction and Friedel-Craft intramolecular cyclization. The position and the length of the alkyl substituents exert a strong effect on the ability of the precursor to undergo electrochemical polymerization. Thus, whereas substitution at the alpha-position of the ethylene linkage (3) results in a rapid inhibition of electropolymerization, introduction of alkyl chains at the beta-position (4, 5) greatly improves the efficiency of the polymerization process. The analysis of the electrochemical and optical properties of the polymers shows that rigidification of the DTE molecule leads to a significant decrease of the oxidation potential and bandgap. A comparative analysis of DTE and its bridged analogues by means of X-ray diffraction reveals, in agreement with experimental and theoretical results, that the observed reduction of both the HOMO-LUMO gap of the precursor and the bandgap of the corresponding polymers are related to a relaxation of bond length alternation in the DTE moiety.

  DOI：

  10.1021/jo9623447

文献信息

• Preparation of substituted bridged indenyl and related ligands
  申请人：Voskoboynikov Z. Alexander

  公开号：US20070135596A1

  公开（公告）日：2007-06-14

  A process for preparing a chelating ligand of the formula (II) from a chelating ligand of the formula (I) via an sp 2 -sp 2 or sp 2 -sp 3 coupling reaction with an organometallic compound of the formula (III). wherein B is a bridging group that is bonded to L 1 and L 2 in formula (I) and to L 3 and L 4 in formula (II); L 1 is a substituted monocyclic or polycyclic ligand that comprises at least one chlorine, bromine, iodine, or sulfonate substituent, directly bonded to an sp 2 carbon atom of the ring structure of the ligand; L 2 is a monoanionic ligand; or L 2 may, independently, be defined as L 1 ; L 3 is the same group as L 1 , but said at least one chlorine, bromine, iodine, or sulfonate substituent is replaced with a hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl fragment; L 4 is the same group as L 2 , though, when L 2 is defined as L 1 , L 4 may be the same as L 3 or L 1 ; R 1 is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl; M 1 is an element of group 1, 2, 12, 13 or 14 of the Periodic Table of the Elements; each X 2 , if present, is selected independently from the group consisting of halogen atoms, the hydroxyl group, alkoxy groups, aryloxy groups, mesylate, tosylate and triflate; r is 1, 2 or 3, and t is 0, 1 or 2, where r+t corresponds to the oxidation number of M 1 .

  从化学配体的公式(I)通过与公式(III)的有机金属化合物进行sp2-sp2或sp2-sp3偶联反应，制备化学配体的公式(II)的方法。其中B是一个桥联基团，与公式(I)中的L1和L2以及公式(II)中的L3和L4结合；L1是一个取代的单环或多环配体，至少包含一个氯、溴、碘或磺酸酯取代基，直接与配体的环结构的sp2碳原子键合；L2是一个单负离子配体；或者L2可以独立地被定义为L1；L3与L1相同，但所述的至少一个氯、溴、碘或磺酸酯取代基被氢化碳基、取代的氢化碳基、卤代碳基或取代的卤代碳基片段所取代；L4与L2相同，但当L2被定义为L1时，L4可以与L3或L1相同；R1是一个氢化碳基、取代的氢化碳基、卤代碳基或取代的卤代碳基；M1是元素周期表第1、2、12、13或14组的元素；每个X2，如果存在，可独立地选择自卤素原子、羟基、烷氧基、芳基氧基、甲磺酸酯、对甲苯磺酸酯和三氟甲磺酸酯组成的群；r为1、2或3，t为0、1或2，其中r+t对应于M1的氧化数。
• Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
  申请人：Voskoboynikov Z. Alexander

  公开号：US20070135623A1

  公开（公告）日：2007-06-14

  Halogen substituted metallocene compounds are described and comprise one or more monocyclic or polycyclic ligands that are pi-bonded to the metal atom and include at least one halogen substituent directly bonded to an sp 2 carbon atom at a bondable ring position of the ligand, wherein the or at least one ligand has one or more ring heteroatoms in its cyclic structure. When combined with a suitable activator, these compounds show activity in the polymerization of olefins, such as ethylene and propylene.

  描述了卤代取代的茂金属化合物，包括一个或多个与金属原子π键结合的单环或多环配体，并且至少包括一个卤素取代基直接键合到配体的可键合环位置上的sp2碳原子，其中该配体或至少一个配体在其环状结构中具有一个或多个环异原子。与适当的活化剂结合时，这些化合物在烯烃聚合反应中显示出活性，例如乙烯和丙烯。
• The Stronger the Better: Donor Substituents Push Catalytic Activity of Molecular Chromium Olefin Polymerization Catalysts
  作者：Helge‐Boj Hansen、Hubert Wadepohl、Markus Enders

  DOI：10.1002/chem.202101586

  日期：2021.8.2

  pyridine-cyclopentadienyl ligands was altered systematically by the introduction of donating groups in the para-position of the pyridine. In the resulting chromium complexes an almost linear correlation between donor strength and the nitrogen-chromium distance as well as the electronic absorption maximum is experimentally observed. The connection of electron-donating groups in the ligand backbone leads to an efficient

  双功能吡啶-环戊二烯基配体的供体强度通过在吡啶的对位引入供体基团而系统地改变。在所得的铬配合物中，实验观察到供体强度与氮-铬距离以及电子吸收最大值之间的几乎线性相关性。配体骨架中给电子基团的连接导致电子影响有效转移到催化活性金属中心，而不会通过空间效应对其进行限制。因此，对于先前研究的催化剂来说，催化烯烃聚合活性已经非常高，通过附加对位-氨基分别连接到螯合吡啶或喹啉。将富含电子的茚基配体与对氨基取代的吡啶结合导致迄今为止对于此类有机铬烯烃聚合催化剂观察到的最高催化活性。所得聚合物具有超高分子量，催化剂结合共聚单体的能力也非常高。
• Constrained geometry complexes of titanium (IV) and zirconium (IV) involving cyclopentadienyl fused to thiophene ring
  作者：Alexey N. Ryabov、Alexander Z. Voskoboynikov

  DOI：10.1016/j.jorganchem.2005.06.011

  日期：2005.10

  geometry complexes (CGCs) of titanium (IV) and zirconium (IV) containing isomeric cyclopentadienyls fused to thiophene fragment, i.e., 4,5-dimethylcyclopenta[b]thienyl and 5,6-dimethylcyclopenta[b]thienyl, have been prepared and unambiguously characterized. The molecular structure of the titanium complex [η5-(5,6-dimethylcyclopenta[b]thienyl)SiMe2(NtBu)-η1]TiCl2 was established by X-ray crystal structure

  制备了钛（IV）和锆（IV）的稠密几何配合物（CGC），它们包含与噻吩片段融合的异构环戊二烯基，即4,5-二甲基环戊[ b ]噻吩基和5,6-二甲基环戊[ b ]噻吩基，并明确地表征。钛络合物的分子结构[η 5 - （5,6- dimethylcyclopenta [ b ]噻吩基）森达2（N吨丁基）-η 1 ]的TiCl 2，通过X射线晶体结构分析确定。初步研究表明，所研究的CGC / MAO为活性烯烃聚合催化剂。
• Heterocyclic metallocenes and polymerization catalysts
  申请人：Ewen A. John

  公开号：US20050192418A1

  公开（公告）日：2005-09-01

  A new class of heterocyclic metallocenes, a catalytic system containing them and a process for polymerizing addition polymerizable monomers using said catalytic system are disclosed; the heterocyclic metallocenes correspond to the formula (I): Y j R″ i Z jj MeQ k P l wherein Y is a coordinating group containing a six π electron central radical directly coordinatng Me, to which are associated one or more radicals containing at least one non-carbon atom selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te; R″ is a divalent bridge between the Y and Z groups; Z is a coordinating group, optionally being equal to Y; Me is a transition metal; Q is halogen or hydrocarbon substituents; P is a counterion; i os 0 or 1; j is 1-3; jj is 0-2; k is 1-3; and l is 0-2.

  本发明公开了一种新型杂环金属茂，一种包含它们的催化体系以及使用所述催化体系聚合加成聚合物单体的方法；所述杂环金属茂对应于式（I）：YjR″iZjjMeQkPl，其中Y是一个配位基团，包含一个直接配位于Me的六π电子中心基团，与之关联的是至少一个含有至少一个非碳原子的基团，所述非碳原子选自B、N、O、Al、Si、P、S、Ga、Ge、As、Se、In、Sn、Sb和Te；R″是Y和Z基团之间的二价桥；Z是一个配位基团，可选地等于Y；Me是一个过渡金属；Q是卤素或碳氢取代基；P是一个反离子；i为0或1；j为1-3；jj为0-2；k为1-3；l为0-2。