ethyl 3-(3-thienyl)-2-butenoate | 65121-25-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 3-(3-thienyl)-2-butenoate
• 英文别名: β-(3-Thienyl)crotonsaeureaethylester；3-thiophen-3-yl-but-2-enoic acid ethyl ester；3-[3]thienyl-ξ-crotonic acid ethyl ester；3-[3]Thienyl-ξ-crotonsaeure-aethylester；Ethyl 3-(thiophen-3-yl)but-2-enoate；ethyl 3-thiophen-3-ylbut-2-enoate
• CAS: 65121-25-7
• 化学式: C₁₀H₁₂O₂S
• 分子量: 196.27
• InChiKey: YRPBGRBSRNQYMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  54.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 3-(3-thienyl)-2-butenoate 在 sodium hydroxide 、 sodium amalgam 、 三氯化铝 、 氯化亚砜 作用下， 以 二硫化碳 、 乙醚 、 乙醇 、 水 为溶剂， 反应 29.0h， 生成 4-methyl-4,5-dihydro-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
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 草酸 作用下， 生成 ethyl 3-(3-thienyl)-2-butenoate
  参考文献：
  名称：

  Carbonyl Derivatives of Thiophene. I. The Reformatsky Reaction with α-Bromoesters

  摘要：

  DOI：

  10.1021/ja01612a036

文献信息

• Cobalt-Catalyzed Diastereo- and Enantioselective Reductive Allyl Additions to Aldehydes with Allylic Alcohol Derivatives via Allyl Radical Intermediates
  作者：Lei Wang、Lifan Wang、Mingxia Li、Qinglei Chong、Fanke Meng

  DOI：10.1021/jacs.1c05690

  日期：2021.8.18

  enantioenriched homoallylic alcohols with a remarkably broad scope of allyl groups that can be introduced. Mechanistic studies indicated that allyl radical intermediates were involved in this process. These new discoveries establish a new strategy for development of enantioselective transformations through capture of radicals by chiral Co complexes, pushing forward the frontier of Co complexes for enantioselective

  催化生成两亲性 π-烯丙基-金属配合物及其在对映选择性转化中的应用构成了将烯丙基引入分子的有效方法。本文提出了一种前所未有的钴催化的高度位点、非对映和对映选择性方案，用于立体选择性形成亲核烯丙基-Co(II) 配合物，然后加入醛。该反应的特点是将容易获得的烯丙醇衍生物非对映和对映收敛转化为多样化的富含对映体的高烯丙醇，其中可以引入的烯丙基范围非常广泛。机理研究表明，烯丙基自由基中间体参与了这一过程。
• 10.1002/cjoc.202400508
  作者：Sun, Gaolei、Wei, Wenhui、Zhao, Xiaowei、Qiao, Baokun、Jiang, Zhiyong

  DOI：10.1002/cjoc.202400508

  日期：——

  high efficiency, displaying excellent compatibility with various functional groups and demonstrating high chemo- and regioselectivity. Mechanistic investigations suggest that consecutive photo-induced electron transfer (ConPET) plays a crucial role in the formation of photocatalyst with greater reducing capability, ultimately enabling the direct reductive conversion of unreactive π-bonds under mild and

  α-Azaarene 季碳中心在药物分子中普遍存在，这使得高效合成方法的开发引起了极大的兴趣。在此，我们描述了一种前所未有的方法，通过采用各种 2,2-二取代环芳基酮与现成的氰基芳烃的光催化还原偶联来构建α全碳季碳中心氮杂烯。该反应以高效率进行，表现出与各种官能团的出色相容性，并表现出高化学选择性和区域选择性。机理研究表明，连续光诱导电子转移 （ConPET） 在具有更强还原能力的光催化剂的形成中起着至关重要的作用，最终能够在温和和无过渡金属的条件下实现未反应性 π 键的直接还原转化。
• Carbonyl Derivatives of Thiophene. I. The Reformatsky Reaction with α-Bromoesters
  作者：Robert D. Schuetz、Wm. H. Houff

  DOI：10.1021/ja01612a036

  日期：1955.4
• Bridged Dithienylethylenes as Precursors of Small Bandgap Electrogenerated Conjugated Polymers
  作者：Philippe Blanchard、Hugues Brisset、Bertrand Illien、Amédée Riou、Jean Roncali

  DOI：10.1021/jo9623447

  日期：1997.4.1

  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.