3,5,5-Trimethyl-2-<(phenylthio)methyl>-2-cyclohexen-1-one | 126319-19-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3,5,5-Trimethyl-2-<(phenylthio)methyl>-2-cyclohexen-1-one
• 英文别名: 3,5,5-Trimethyl-2-(phenylsulfanylmethyl)cyclohex-2-en-1-one
• CAS: 126319-19-5
• 化学式: C₁₆H₂₀OS
• 分子量: 260.4
• InChiKey: WEVFDEDLUSDZMJ-UHFFFAOYSA-N

物化性质

• 沸点：
  371.6±31.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,5,5-Trimethyl-2-<(phenylthio)methyl>-2-cyclohexen-1-one 在 Oxone 、 samarium diiodide 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 71.05h， 生成 2,2,4,6,6-Pentamethyl-3,5,6,7-tetrahydro-2H-indole 1-oxide
  参考文献：
  名称：

  A New Synthesis of .alpha.-Asymmetric Nitroxide Radicals

  摘要：

  A new methodology for the synthesis of cl-asymmetric bicyclic nitroxides is described. Reduction of certain homoallylic nitroenone with 3.0 equiv of SmI2 in THF or THF-Et(2)O at -50 degrees C gave a stable nitroxide radical-enolate intermediate, a kind of radical-anion species. The subsequent addition of electrophiles such as acyl chlorides at -50 degrees C resulted in the O-acylation of the enolate moiety to form the corresponding neutral nitroxide radical. The reduction process was quite sensitive to the substrate structure, amount of SmI2, solvent composition, and reaction temperature. The optimum reaction conditions for this two-step reaction were determined. Analytically pure stable nitroxide radicals were isolated in good to fair yields when benzoyl chlorides substituted by electron-withdrawing groups were used as the electrophile for O-acylation. Although the use of organosilyl chlorides and alkylating reagents as the electrophile seemed to provide the corresponding radical products in the reaction mixture, pure radical products were not obtained. The mechanism of formation of the nitroxide radical-enolate intermediate was investigated by EPR spectroscopy and the product analysis.

  DOI：

  10.1021/jo00126a035
• 作为产物：
  描述：

  聚合甲醛 、 异佛尔酮 、 苯硫酚 在 三乙醇胺 作用下， 以 水 为溶剂， 反应 4.0h， 生成 3,5,5-Trimethyl-2-<(phenylthio)methyl>-2-cyclohexen-1-one
  参考文献：
  名称：

  A New Synthesis of .alpha.-Asymmetric Nitroxide Radicals

  摘要：

  A new methodology for the synthesis of cl-asymmetric bicyclic nitroxides is described. Reduction of certain homoallylic nitroenone with 3.0 equiv of SmI2 in THF or THF-Et(2)O at -50 degrees C gave a stable nitroxide radical-enolate intermediate, a kind of radical-anion species. The subsequent addition of electrophiles such as acyl chlorides at -50 degrees C resulted in the O-acylation of the enolate moiety to form the corresponding neutral nitroxide radical. The reduction process was quite sensitive to the substrate structure, amount of SmI2, solvent composition, and reaction temperature. The optimum reaction conditions for this two-step reaction were determined. Analytically pure stable nitroxide radicals were isolated in good to fair yields when benzoyl chlorides substituted by electron-withdrawing groups were used as the electrophile for O-acylation. Although the use of organosilyl chlorides and alkylating reagents as the electrophile seemed to provide the corresponding radical products in the reaction mixture, pure radical products were not obtained. The mechanism of formation of the nitroxide radical-enolate intermediate was investigated by EPR spectroscopy and the product analysis.

  DOI：

  10.1021/jo00126a035

文献信息

• Novel radical chain substitution reaction involving single electron transfer SET processes
  作者：Rui Tamura、Kunihiko Yamawaki、Nagao Azuma

  DOI：10.1021/jo00020a004

  日期：1991.9

  Beta-Substituted alpha[(phenylsulfonyl)methyl]- and alpha-z[(phenylthio)methyl]cyclohexenones 1-4 underwent regioselective replacement of the sulfonyl and sulfenyl groups by stabilized carbanions such as LiCMe2NO2 mainly by a radical chain mechanism, which was confirmed by investigating the effects of photoirradiation, radical scavengers, and reaction solvents and by the ESR and spectroscopic studies.