3-Methyl-2-(2-methyl-2-nitro-propyl)-cyclohex-2-enone | 132475-89-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Methyl-2-(2-methyl-2-nitro-propyl)-cyclohex-2-enone
• 英文别名: 3-Methyl-2-(2-methyl-2-nitropropyl)cyclohex-2-en-1-one
• CAS: 132475-89-9
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: MZQOLIYHICSBFY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Methyl-2-(2-methyl-2-nitro-propyl)-cyclohex-2-enone 、 3,5-二硝基苯甲酰氯 在 samarium diiodide 作用下， 生成
  参考文献：
  名称：

  Tamura, Rui; Susuki, Shinsuke; Azuma, Nagao, Angewandte Chemie, 1994, vol. 106, # 8, p. 919 - 921

  摘要：

  DOI：
• 作为产物：
  描述：

  2-lithio-2-nitropropane 、 3-Methyl-2-(nitromethyl)-2-cyclohexen-1-one 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 以60%的产率得到3-Methyl-2-(2-methyl-2-nitro-propyl)-cyclohex-2-enone
  参考文献：
  名称：

  亲核试剂选择性取代环状α-（硝基烷基）-或α-（苯磺酰基烷基）烯酮中的硝基或磺酰基

  摘要：

  环状α-（硝基烷基）烯酮和α-（苯磺酰基烷基）烯酮通过相对较软的硫，氮和碳亲核试剂对硝基进行区域选择性取代。

  DOI：

  10.1016/s0040-4020(01)89067-0

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.
• Preparation and Properties of Chiral Nitroxide Radicals with Helical Crystal Structure
  作者：Rui Tamura、Shinsuke Susuki、Nagao Azuma、Akira Matsumoto、Fumio Toda、Takeji Takui、Daisuke Shiomi、Koichi Itoh

  DOI：10.1080/10587259508034041

  日期：1995.9

  A new type of alpha-asymmetric bicyclic nitroxides were synthesized by three electron reduction of certain homoallylic nitroenones followed by the reaction with nitro-substituted benzoyl chlorides. Some nitroxides thus obtained turned out to exist as a conglomerate (racemic mixture), an equimolecular mixture of two crystalline enantiomers, and hence induced spontaneous optical resolution upon recrystallization. The relationship between the formation of conglomerates and their molecular and crystral structures is described, together with the preliminary results of their paramagnetic susceptibility mesurements.
• 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.