(S)-2-nitropentan-3-one

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (S)-2-nitropentan-3-one
• 英文别名: (2S)-2-nitropentan-3-one
• 化学式: C₅H₉NO₃
• 分子量: 131.131
• InChiKey: QKSLOOGJRHJRIJ-BYPYZUCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (R)-2-nitropentan-3-one 在 6-O-(t-BuPh2Si)-2,3-di-O-acetyl-β-cyclodextrin 作用下， 生成 (S)-2-nitropentan-3-one
  参考文献：
  名称：

  Enantiomerization Study of Some α-Nitroketones by Dynamic High-Resolution Gas Chromatography

  摘要：

  The kinetics of the reversible enantiomer interconversion of 3-nitrobutan-2-one (1), 3-nitropentan2-one (2), and 2-nitropentan-3-one (3) have been studied by dynamic high-resolution gas chromatography (DHRGC) by using a P-cyclodextrin derivative chiral stationary phase; the process occurs via enolization of the keto forms. The DHRGC experiments involving the studied nitroketones and the chiral stationary phase show chromatographic profiles with a typical interconversion plateau in the temperature range between 130 and 160 degreesC. Computer simulation of the experimental chromatographic elution profiles was employed for the determination of rate constants and the corresponding enantiomerization barriers (k, DeltaG(#)(T), DeltaH(#), and DeltaS(#)). The highly negative entropy of activation (AS(#) values from -19 to -37 cal mol(-1) K-1) points to a transition state (TS) with large charge separation. The obtained results for 1-3 show the dramatic effect of an alpha-nitrosubstituent on the rate of enolization of simple ketones, when compared with those for 3-chloro-2-butanone and 3-methyl-2-pentanone. To get some information on the separate contributions of the stationary liquid phase and the mobile gas phase on the studied process, some DFT ab initio calculations have been performed for the same compounds.

  DOI：

  10.1021/jo0267302

文献信息

• Enantiomerization Study of Some α-Nitroketones by Dynamic High-Resolution Gas Chromatography
  作者：Francesco Gasparrini、Marco Pierini、Claudio Villani、Paolo De Maria、Antonella Fontana、Roberto Ballini

  DOI：10.1021/jo0267302

  日期：2003.4.1

  The kinetics of the reversible enantiomer interconversion of 3-nitrobutan-2-one (1), 3-nitropentan2-one (2), and 2-nitropentan-3-one (3) have been studied by dynamic high-resolution gas chromatography (DHRGC) by using a P-cyclodextrin derivative chiral stationary phase; the process occurs via enolization of the keto forms. The DHRGC experiments involving the studied nitroketones and the chiral stationary phase show chromatographic profiles with a typical interconversion plateau in the temperature range between 130 and 160 degreesC. Computer simulation of the experimental chromatographic elution profiles was employed for the determination of rate constants and the corresponding enantiomerization barriers (k, DeltaG(#)(T), DeltaH(#), and DeltaS(#)). The highly negative entropy of activation (AS(#) values from -19 to -37 cal mol(-1) K-1) points to a transition state (TS) with large charge separation. The obtained results for 1-3 show the dramatic effect of an alpha-nitrosubstituent on the rate of enolization of simple ketones, when compared with those for 3-chloro-2-butanone and 3-methyl-2-pentanone. To get some information on the separate contributions of the stationary liquid phase and the mobile gas phase on the studied process, some DFT ab initio calculations have been performed for the same compounds.