3-([13C]-methyl)cyclohexanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-([13C]-methyl)cyclohexanone
• 英文别名: 3-(113C)methylcyclohexan-1-one
• 化学式: C₇H₁₂O
• 分子量: 113.161
• InChiKey: UJBOOUHRTQVGRU-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-([13C]-methyl)cyclohexanone 、 二硫化碳 、 碘甲烷 在 正丁基锂 、 2,6-二叔丁基-4-甲基苯酚 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 21.5h， 以29%的产率得到2-[bis(methylthio)methylene]-5-([13C]-methyl)cyclohexanone
  参考文献：
  名称：

  On the Mechanism of the Skraup−Doebner−Von Miller Quinoline Synthesis

  摘要：

  The mechanism of the formation of substituted quinolines from anilines and alpha,beta-unsaturated ketones has been studied by the use of C-13-labeled ketones in cross-over experiments. In the reaction of doubly labeled C-13(2,4) mesityl oxide, a 100% scrambling of the label in the quinoline product was observed, whereas only a small (5-10%) amount of the starting mesityl oxide showed scrambling of the label. Similarly, the reaction of triply labeled pulegone clearly shows that the label in the product is 100% scrambled, whereas the label in the starting pulegone is retained. On the basis of these studies, a mechanistic pathway for the Skraup quinoline synthesis is proposed that involves a fragmentation-recombination mechanism. The aniline component condenses with the alpha,beta-unsaturated ketone initially in a conjugate fashion, followed by a fragmentation to the corresponding imine and the ketone itself. These fragments recombine to form the quinoline product.

  DOI：

  10.1021/jo052410h
• 作为产物：
  描述：

  2-环己烯-1-酮 、 [13C]-methyl lithium 在 苯硫酚铜(I) 作用下， 以 乙醚 为溶剂， 以72%的产率得到3-([13C]-methyl)cyclohexanone
  参考文献：
  名称：

  On the Mechanism of the Skraup−Doebner−Von Miller Quinoline Synthesis

  摘要：

  The mechanism of the formation of substituted quinolines from anilines and alpha,beta-unsaturated ketones has been studied by the use of C-13-labeled ketones in cross-over experiments. In the reaction of doubly labeled C-13(2,4) mesityl oxide, a 100% scrambling of the label in the quinoline product was observed, whereas only a small (5-10%) amount of the starting mesityl oxide showed scrambling of the label. Similarly, the reaction of triply labeled pulegone clearly shows that the label in the product is 100% scrambled, whereas the label in the starting pulegone is retained. On the basis of these studies, a mechanistic pathway for the Skraup quinoline synthesis is proposed that involves a fragmentation-recombination mechanism. The aniline component condenses with the alpha,beta-unsaturated ketone initially in a conjugate fashion, followed by a fragmentation to the corresponding imine and the ketone itself. These fragments recombine to form the quinoline product.

  DOI：

  10.1021/jo052410h

文献信息

• On the Mechanism of the Skraup−Doebner−Von Miller Quinoline Synthesis
  作者：Scott E. Denmark、Srikanth Venkatraman

  DOI：10.1021/jo052410h

  日期：2006.2.1

  The mechanism of the formation of substituted quinolines from anilines and alpha,beta-unsaturated ketones has been studied by the use of C-13-labeled ketones in cross-over experiments. In the reaction of doubly labeled C-13(2,4) mesityl oxide, a 100% scrambling of the label in the quinoline product was observed, whereas only a small (5-10%) amount of the starting mesityl oxide showed scrambling of the label. Similarly, the reaction of triply labeled pulegone clearly shows that the label in the product is 100% scrambled, whereas the label in the starting pulegone is retained. On the basis of these studies, a mechanistic pathway for the Skraup quinoline synthesis is proposed that involves a fragmentation-recombination mechanism. The aniline component condenses with the alpha,beta-unsaturated ketone initially in a conjugate fashion, followed by a fragmentation to the corresponding imine and the ketone itself. These fragments recombine to form the quinoline product.