N-methyl-N-(thiophen-3-yl)formamide | 106943-91-3

• 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: N-methyl-N-(thiophen-3-yl)formamide
• 英文别名: N-Methyl-N-thiophen-3-yl-formamide；N-methyl-N-thiophen-3-ylformamide
• CAS: 106943-91-3
• 化学式: C₆H₇NOS
• 分子量: 141.194
• InChiKey: HKNSLNWVZVEMNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methyl-N-(thiophen-3-yl)formamide 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以90%的产率得到N,N-dimethyl thienyl-3 amine
  参考文献：
  名称：

  3-（N-烷基氨基）噻吩的电化学研究：氧化聚合的独特机理的实验和理论见解。

  摘要：

  可以通过电聚合产生许多共轭聚合物体系，包括聚噻吩和聚苯胺。虽然已经报道两者都通过自由基偶联在阳极上聚合，但是苯胺氮的存在在电聚合机理中起着重要作用。在这项研究中，利用实验和理论方法研究了3-（N-烷基氨基）噻吩的电聚合机理，这是噻吩和苯胺的结构杂化物。合成新型短链3-（N讨论了-烷基氨基）噻吩，并提出了电聚合机理，其中通过除去氮孤对电子而发生氧化，然后进行化学步骤，导致在噻吩环的2位上产生自由基。这些最终自由基阳离子的偶联因此产生典型的聚（α-α'-噻吩）骨架。

  DOI：

  10.1021/jp912287s
• 作为产物：
  描述：

  3-溴噻吩 、 N-甲基甲酰胺 在 potassium phosphate 、 copper(l) iodide 、 1,2-二氨基环己烷 作用下， 以 1,4-二氧六环 为溶剂， 以90%的产率得到N-methyl-N-(thiophen-3-yl)formamide
  参考文献：
  名称：

  3-（N-烷基氨基）噻吩的电化学研究：氧化聚合的独特机理的实验和理论见解。

  摘要：

  可以通过电聚合产生许多共轭聚合物体系，包括聚噻吩和聚苯胺。虽然已经报道两者都通过自由基偶联在阳极上聚合，但是苯胺氮的存在在电聚合机理中起着重要作用。在这项研究中，利用实验和理论方法研究了3-（N-烷基氨基）噻吩的电聚合机理，这是噻吩和苯胺的结构杂化物。合成新型短链3-（N讨论了-烷基氨基）噻吩，并提出了电聚合机理，其中通过除去氮孤对电子而发生氧化，然后进行化学步骤，导致在噻吩环的2位上产生自由基。这些最终自由基阳离子的偶联因此产生典型的聚（α-α'-噻吩）骨架。

  DOI：

  10.1021/jp912287s

文献信息

• Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
  申请人：——

  公开号：US20030065187A1

  公开（公告）日：2003-04-03

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在酰胺或胺基团的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在酰基肼的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在另一些实施例中，本发明涉及铜催化的方法，用于在含氮杂环芳烃（例如吲哚、吡唑和吲哌）的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在醇的氧原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子的反应物（例如烯醇酸盐或丙二酸盐负离子）与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价。
• Copper/N,N-Dimethylglycine Catalyzed Goldberg Reactions Between Aryl Bromides and Amides, Aryl Iodides and Secondary Acyclic Amides
  作者：Liqin Jiang

  DOI：10.3390/molecules190913448

  日期：——

  copper-catalyzed Goldberg reaction at 90–110 °C between aryl bromides and amides providing the desired products in good to excellent yields has been developed using N,N-dimethylglycine as the ligand. The reaction is tolerant toward a wide range of amides and a variety of functional group substituted aryl bromides. In addition, hindered, unreactive aromatic and aliphatic secondary acyclic amides, known to be poor

  使用 N,N-二甲基甘氨酸作为配体，在 90–110°C 下，芳基溴化物和酰胺之间进行了有效且通用的铜催化 Goldberg 反应，以良好至优异的收率提供所需产物。该反应对多种酰胺和多种官能团取代的芳基溴化物具有耐受性。此外，受阻的、非反应性的芳香族和脂肪族仲无环酰胺（已知为不良亲核试剂）可通过这种简单且廉价的铜/N,N-二甲基甘氨酸催化体系与芳基碘有效偶联。
• Copper-catalyzed formation of carbon heteroatom and carbon-carbon bonds
  申请人：Buchwald L. Stephen

  公开号：US20050215794A1

  公开（公告）日：2005-09-29

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和酰胺或胺基团的氮原子之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和酰肼的氮原子之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和含氮杂环芳香族化合物（例如吲哚、吡唑和吲唑）的氮原子之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和醇的氧原子之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子（例如烯醇酸根离子或马隆酸根离子）的反应物和苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价易行。
• Copper-catalyzed formation of carbon-heteroatom and carbon—carbon bonds
  申请人：Buchwald Stephen L.

  公开号：US09067955B2

  公开（公告）日：2015-06-30

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods, such as the reaction of Z-X with C(L)(R)(R′)2 in the present of a catalyst and a base, thereby forming C(Z)(R)(R′)2; wherein X represents I, Cl, alkylsulfonate, or arylsulfonate; Z represents optionally substituted aryl, heteroaryl or alkenyl; L represents H or a negative charge; catalyst comprises a copper atom or ion, and a ligand, wherein the ligand is an optionally substituted aryl alcohol, alkyl amine, 1,2-diamine, 1,2-aminoalcohol, 1,2-diol, imidazolium carbene, pyridine, or 1,10-phenanthroline; the ligand is a chelating ligand; and the base represents a Bronsted base; R represents H, optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; R′ represents independently for each occurrence H, alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl, formyl, acyl, —CO2R″, —C(O)N(R)2, sulfonyl, —P(O)(OR″)2, —CN, or —NO2; R″ represents independently for each occurrence optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; and C(R′)2(R) taken together may represent nitrile.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法，例如在催化剂和碱的存在下，Z-X与C（L）（R）（R'）2反应，从而形成C（Z）（R）（R'）2；其中X代表I，Cl，烷基磺酸盐或芳基磺酸盐；Z代表可选取代的芳基，杂原芳基或烯丙基；L代表H或负电荷；催化剂包括铜原子或离子和配体，其中配体是可选取代的芳基醇，烷基胺，1,2-二胺，1,2-氨基醇，1,2-二醇，咪唑卡宾，吡啶或1,10-菲啰啉；配体是螯合配体；碱代表布朗斯特德碱；R代表H，可选取代的烷基，环烷基，芳基烷基，芳基或杂原芳基；R'代表独立地为每个出现的H，烷基，环烷基，芳基烷基，芳基或杂原芳基，甲酰基，酰基，-CO2R″，-C（O）N（R）2，磺酰基，-P（O）（OR″）2，-CN或-NO2；R″代表独立地为每个出现的可选取代的烷基，环烷基，芳基烷基，芳基或杂原芳基；而C（R'）2（R）在一起可以代表腈。
• Ligand-Enabled Ni–Al Bimetallic Catalysis for Nonchelated Dual C–H Annulation of Arylformamides and Alkynes
  作者：Yin-Xia Wang、Feng-Ping Zhang、Yu-Xin Luan、Mengchun Ye

  DOI：10.1021/acs.orglett.0c00432

  日期：2020.3.20

  A bifunctional secondary phosphine oxide (SPO) ligand-controlled method was developed for Ni-Al-catalyzed nonchelated dual C-H annulation of arylformamides with alkynes, providing a series of substituted amide-containing heterocycles in <= 97% yield. The SPO-bound bimetallic catalysis proved to be critical to the reaction efficiency.