5,5-Dimethyl-3-hydroxy-2-(2-methyl-2-nitropropyl)-2-cyclohexen-1-one | 171112-76-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-Dimethyl-3-hydroxy-2-(2-methyl-2-nitropropyl)-2-cyclohexen-1-one
• 英文别名: 3-Hydroxy-5,5-dimethyl-2-(2-methyl-2-nitropropyl)cyclohex-2-en-1-one
• CAS: 171112-76-8
• 化学式: C₁₂H₁₉NO₄
• 分子量: 241.287
• InChiKey: RDYHHSWRAOWBJI-UHFFFAOYSA-N

物化性质

• 沸点：
  364.9±42.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,5-Dimethyl-3-hydroxy-2-(2-methyl-2-nitropropyl)-2-cyclohexen-1-one 在 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 5,5-Dimethyl-2-(2-methyl-2-nitropropyl)-3-phenylcyclohex-2-en-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
• 作为产物：
  描述：

  5,5-Dimethyl-3-hydroxy-2-<(phenylsulfonyl)methyl>-2-cyclohexen-1-one 在 硫酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 75.02h， 生成 5,5-Dimethyl-3-hydroxy-2-(2-methyl-2-nitropropyl)-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

• A New Synthesis of .alpha.-Asymmetric Nitroxide Radicals
  作者：Rui Tamura、Shinsuke Susuki、Nagao Azuma、Akira Matsumoto、Fumio Toda、Yasutaka Ishii

  DOI：10.1021/jo00126a035

  日期：1995.10

  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.