2-(1-trimethylsiloxybutyl)-cyclohexanone | 146860-49-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-(1-trimethylsiloxybutyl)-cyclohexanone
• 英文别名: 2-(1-Trimethylsilyloxybutyl)cyclohexan-1-one
• CAS: 146860-49-3
• 化学式: C₁₃H₂₆O₂Si
• 分子量: 242.434
• InChiKey: RSDJTOALMLVZQI-UHFFFAOYSA-N

物化性质

• 沸点：
  285.0±13.0 °C(Predicted)
• 密度：
  0.921±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1-trimethylsiloxybutyl)-cyclohexanone 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 Cyclohexanone, 2-(1-hydroxybutyl)-
  参考文献：
  名称：

  New effective catalysts for Mukaiyama-aldol and -Michael reactions: bismuth trichloride-metallic iodide systems

  摘要：

  Metallic iodide-activated bismuth(III) chloride efficiently catalyzes the Mukaiyama-Aldol and -Michael reactions. Some examples of reactions of silyl enol ethers derived from acetophenone and cyclohexanone (I and 2, respectively) with aldehydes, ketones, acetals, and alpha-enones are given. The cross-over aldolization between 1 and benzaldehyde in the presence of BiCl3-l.5ZnI2 or BiCl3-1.5SnI2 systems (5 % mol) has been carried out quantitatively at -30 and -78-degrees-C, respectively. For this reaction a similar activation has been also observed with antimony(III) chloride. X-ray patterns of catalytic systems show the formation of bismuth(III) iodide by CI/I-exchange reaction between BiCl3 and metallic iodide (NaI, ZnI2, SnI2,...). These results.have been rationalized with a two-step mechanism in which a key feature seems to be the activating role played by BiI3 toward the cleavage of the Bi-chelate intermediate by the chlorosilane formed. Ultrasound activates significantly the catalytic power of these metallic halide systems.

  DOI：

  10.1021/jo00059a040
• 作为产物：
  描述：

  1-环己烯氧基三甲基硅烷 、 正丁醛 在 bismuth(III) chloride 、 zinc(II) iodide 作用下， 以 二氯甲烷 为溶剂， 生成 2-(1-trimethylsiloxybutyl)-cyclohexanone
  参考文献：
  名称：

  New effective catalysts for Mukaiyama-aldol and -Michael reactions: bismuth trichloride-metallic iodide systems

  摘要：

  Metallic iodide-activated bismuth(III) chloride efficiently catalyzes the Mukaiyama-Aldol and -Michael reactions. Some examples of reactions of silyl enol ethers derived from acetophenone and cyclohexanone (I and 2, respectively) with aldehydes, ketones, acetals, and alpha-enones are given. The cross-over aldolization between 1 and benzaldehyde in the presence of BiCl3-l.5ZnI2 or BiCl3-1.5SnI2 systems (5 % mol) has been carried out quantitatively at -30 and -78-degrees-C, respectively. For this reaction a similar activation has been also observed with antimony(III) chloride. X-ray patterns of catalytic systems show the formation of bismuth(III) iodide by CI/I-exchange reaction between BiCl3 and metallic iodide (NaI, ZnI2, SnI2,...). These results.have been rationalized with a two-step mechanism in which a key feature seems to be the activating role played by BiI3 toward the cleavage of the Bi-chelate intermediate by the chlorosilane formed. Ultrasound activates significantly the catalytic power of these metallic halide systems.

  DOI：

  10.1021/jo00059a040

文献信息

• New effective catalysts for Mukaiyama-aldol and -Michael reactions: bismuth trichloride-metallic iodide systems
  作者：Christophe Le Roux、Hafida Gaspard-Iloughmane、Jacques Dubac、Joel Jaud、Pierre Vignaux

  DOI：10.1021/jo00059a040

  日期：1993.3

  Metallic iodide-activated bismuth(III) chloride efficiently catalyzes the Mukaiyama-Aldol and -Michael reactions. Some examples of reactions of silyl enol ethers derived from acetophenone and cyclohexanone (I and 2, respectively) with aldehydes, ketones, acetals, and alpha-enones are given. The cross-over aldolization between 1 and benzaldehyde in the presence of BiCl3-l.5ZnI2 or BiCl3-1.5SnI2 systems (5 % mol) has been carried out quantitatively at -30 and -78-degrees-C, respectively. For this reaction a similar activation has been also observed with antimony(III) chloride. X-ray patterns of catalytic systems show the formation of bismuth(III) iodide by CI/I-exchange reaction between BiCl3 and metallic iodide (NaI, ZnI2, SnI2,...). These results.have been rationalized with a two-step mechanism in which a key feature seems to be the activating role played by BiI3 toward the cleavage of the Bi-chelate intermediate by the chlorosilane formed. Ultrasound activates significantly the catalytic power of these metallic halide systems.
• BiCl3-catalyzed Mukaiyama-aldol and carbonyl-ene reactions
  作者：Laurence Peidro、Christophe Le Roux、André Laporterie、Jacques Dubac

  DOI：10.1016/0022-328x(96)06229-8

  日期：1996.8

  The H-ene pathway has not been detected for the bismuth(III) chloride-catalyzed Mukaiyama-aldol reaction involving silyl enol ethers and aldehydes. The silatropic ene-like process is the only mechanism observed, even with the weakly reactive 1-(trimethylsilyloxy) cyclohexene. However, trimerization of an aliphatic aldehyde can occur.