3,5-bis(N-acetyl-N-methylaminomethyl)-2-methoxythiophene | 1261063-31-3

• 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: 3,5-bis(N-acetyl-N-methylaminomethyl)-2-methoxythiophene
• 英文别名: N-[[4-[[acetyl(methyl)amino]methyl]-5-methoxythiophen-2-yl]methyl]-N-methylacetamide
• CAS: 1261063-31-3
• 化学式: C₁₃H₂₀N₂O₃S
• 分子量: 284.379
• InChiKey: NQDRSMJOTPDKKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  78.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-甲氧基噻吩 、 N,N-二甲基乙酰胺 在 iron(III) chloride 、 二叔丁基过氧化物 作用下， 以 1,2-二氯-2-甲基丙烷 为溶剂， 反应 26.0h， 生成 N-[(5-methoxy-2-thienyl)methyl]-N-methylacetamide 、 N-[(2-methoxy-3-thienyl)methyl]-N-methylacetamide 、 3,5-bis(N-acetyl-N-methylaminomethyl)-2-methoxythiophene
  参考文献：
  名称：

  Iron-Catalyzed Oxidative Coupling of Alkylamides with Arenes through Oxidation of Alkylamides Followed by Friedel−Crafts Alkylation

  摘要：

  FeCL(3) in combination with t-BuOOt-Bu as an oxidant was found to be an efficient catalyst for oxidation of alkylamides to alpha-(tert-butoxy)alkylamides. FeCl(2) and CuCl showed, respectively, almost the same and slightly lower activities compared with FeCl(3) in the tert-butoxylation of N-phenylpyrrolidone (1a), whereas no tert-butoxylated product was obtained by use of Fe(OTf)(3), RuCl(3), or Zr(OTf)(4). FeCl(3) was found to be effective also as a catalyst for the Friedel-Crafts alkylation with thus obtained alpha-(tert-butoxy)alkylamides. The Friedel-Crafts alkylation proceeded smoothly also in the presence of a catalytic amount of Fe(OTf)(3), RuCl(3), or Zr(OTf)(4). In contrast, FeCl(2) and CuCl, which showed certain activity toward the tert-butoxylation, failed to promote the Friedel Crafts alkylation. Among the transition metal complexes thus far examined, only FeCl(3) showed high catalytic activities for both the oxidation and the Friedel-Crafts alkylation. The bifunctionality of FeCl(3) was utilized for the oxidative coupling of alkylamides with arenes through a tandem reaction consisting of oxidation of alkylamides to alpha-(tert-butoxy)alkylamides and the following Friedel-Crafts alkylation. The FeCl(3)-catalyzed oxidative coupling is applicable to a wide variety of alkylamides and arenes, though a combination of FeCl(3) with Fe(OTf)(3) was found to be effective for the reaction of arenes with low nucleophilicity. A Fe(II)-Fe(III) catalytic cycle is concerned with the tert-butoxylation, whereas a Fe(III) complex as a Lewis acid catalyzes the Friedel-Crafts alkylation.

  DOI：

  10.1021/jo102217m

文献信息

• Iron-Catalyzed Oxidative Coupling of Alkylamides with Arenes through Oxidation of Alkylamides Followed by Friedel−Crafts Alkylation
  作者：Eiji Shirakawa、Nanase Uchiyama、Tamio Hayashi

  DOI：10.1021/jo102217m

  日期：2011.1.7

  FeCL(3) in combination with t-BuOOt-Bu as an oxidant was found to be an efficient catalyst for oxidation of alkylamides to alpha-(tert-butoxy)alkylamides. FeCl(2) and CuCl showed, respectively, almost the same and slightly lower activities compared with FeCl(3) in the tert-butoxylation of N-phenylpyrrolidone (1a), whereas no tert-butoxylated product was obtained by use of Fe(OTf)(3), RuCl(3), or Zr(OTf)(4). FeCl(3) was found to be effective also as a catalyst for the Friedel-Crafts alkylation with thus obtained alpha-(tert-butoxy)alkylamides. The Friedel-Crafts alkylation proceeded smoothly also in the presence of a catalytic amount of Fe(OTf)(3), RuCl(3), or Zr(OTf)(4). In contrast, FeCl(2) and CuCl, which showed certain activity toward the tert-butoxylation, failed to promote the Friedel Crafts alkylation. Among the transition metal complexes thus far examined, only FeCl(3) showed high catalytic activities for both the oxidation and the Friedel-Crafts alkylation. The bifunctionality of FeCl(3) was utilized for the oxidative coupling of alkylamides with arenes through a tandem reaction consisting of oxidation of alkylamides to alpha-(tert-butoxy)alkylamides and the following Friedel-Crafts alkylation. The FeCl(3)-catalyzed oxidative coupling is applicable to a wide variety of alkylamides and arenes, though a combination of FeCl(3) with Fe(OTf)(3) was found to be effective for the reaction of arenes with low nucleophilicity. A Fe(II)-Fe(III) catalytic cycle is concerned with the tert-butoxylation, whereas a Fe(III) complex as a Lewis acid catalyzes the Friedel-Crafts alkylation.