3,5,5-Trimethyl-2-<(phenylsulfonyl)methyl>-2-cyclohexen-1-one | 135823-73-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,5,5-Trimethyl-2-<(phenylsulfonyl)methyl>-2-cyclohexen-1-one
• 英文别名: 3,5,5-trimethyl-2-(phenylsulfonylmethyl)-2-cyclohexen-1-one；2-(Benzenesulfonylmethyl)-3,5,5-trimethylcyclohex-2-en-1-one
• CAS: 135823-73-3
• 化学式: C₁₆H₂₀O₃S
• 分子量: 292.399
• InChiKey: RBDILBKPTIZSIL-UHFFFAOYSA-N

物化性质

• 沸点：
  460.3±38.0 °C(Predicted)
• 密度：
  1.133±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 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：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,5,5-Trimethyl-2-<(phenylsulfonyl)methyl>-2-cyclohexen-1-one 在 samarium diiodide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 71.17h， 生成
  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：

  异佛尔酮 在 Oxone 、 三乙醇胺 作用下， 以 甲醇 、 水 为溶剂， 反应 5.0h， 生成 3,5,5-Trimethyl-2-<(phenylsulfonyl)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

• Molecular and Crystal Structure of 3,5,5-Trimethyl-2-(2-methyl-2-nitropropyl)-2-cyclohexen-1-one Possessing Molecular Asymmetry
  作者：Nagao Azuma、Takehiro Ozawa、Kunihiko Yamawaki、Rui Tamura

  DOI：10.1246/bcsj.65.2860

  日期：1992.10

  The crystal structure of an aliphatic nitro compound with atropisomerism, C13H21NO3, has been determined by X-ray diffraction at ambient temperature. The monoclinic structure (P21/c, Z = 8) was refined by the full-matrix least-squares method to a final R = 0.040 for 2394 observed unique reflections. Two crystallographically independent molecules consist of a pair of atropisomers. The intramolecular O···H–C type hydrogen bonds (O···C(methyl): 3.21–3.54 Å) and the contact between the nitro oxygen and ethylenic carbon atoms (O···C: 3.24 and 3.36 Å) may be responsible for this isomerism.

  在室温下，通过X射线衍射确定了具有旋光异构性的脂肪族硝基化合物C13H21NO3的水晶结构。通过全矩阵最小二乘法，将单斜晶系（P21/c，Z = 8）的2394个观察到的独特反射最终精炼为R = 0.040。一对旋光异构体由两个晶体学上独立的分子组成。分子内O···H-C型氢键（O···C（甲基）：3.21-3.54 Å）以及硝基氧和乙烯基碳原子之间的接触（O···C：3.24和3.36 Å）可能是这种异构性的原因。
• Synthesis of α,α'-Asymmetric Nitroxide Radicals by C- or O-Acylation of Radical-enolate Intermediates Generated by Reduction of Homoallylic Nitro Enones with Samarium(II) Iodide
  作者：Rui Tamura、Satoshi Shimono、Kasuke Fujita、Ken-ichi Hirao

  DOI：10.3987/com-00-s(i)19

  日期：——

  A new synthetic method to form two structurally different alpha, alpha'-asymmetric bicyclic nitroxides from the same substrate is described. Reduction of certain homoallylic nitro enones bearing a long alkyl chain with 3.0 equiv of SmI2 in THF at -78 degreesC gave a nitroxide radical-anion species of type A, while the same reduction followed by addition of HMPA at -78 degreesC resulted in the isomerization of the double bond to afford a different nitroxide radical anion species of type C. The former radical-anion undergoes O-acylation by the reaction with acyl chlorides to give alpha, alpha'-asymmetric bicyclic ester-nitroxides of type B, while the latter one does C-acylation to produce alpha, alpha'-asymmetric bicyclic beta -diketo nitroxides of type D.
• 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.