N-phenacyl-4-cyanopyridinium ylide | 25357-51-1

• 英文名称: N-phenacyl-4-cyanopyridinium ylide
• 英文别名: N-Phenacyl-4-cyanpyridinium-ylid
• CAS: 25357-51-1
• 化学式: C₁₄H₁₀N₂O
• 分子量: 222.246
• InChiKey: QDVRDQXXGVGRMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  N-phenacyl-4-cyanopyridinium ylide 、 1-(4-甲基苯基)-1H-吡咯-2,5-二酮 以100%的产率得到
  参考文献：
  名称：

  TSUGE, OTOHIKO;KANEMASA, SHUJI;TAKENAKA, SHIGEORI;KURAOKA, SATORU, CHEM. LETT., 1984, N 3, 465-468

  摘要：

  DOI：
• 作为产物：
  描述：

  N-phenacyl-4-cyanopyridinium bromide 在 三乙烯二胺 作用下， 以 水 为溶剂， 生成 N-phenacyl-4-cyanopyridinium ylide
  参考文献：
  名称：

  Deprotonation of N-phenacyl- and N-acetonyl-4-cyanopyridinium halides with 1,4-diazabicyclo[2,2,2]octane

  摘要：

  In N-phenacyl- and N-acetonyl-4-cyanopyridinium halides (1a.Br and 1b.Cl) the N+CH2 hydrogens are replaced by deuterium in D2O or CH3OD solutions, similarly as in beta-diketones, proving a prototropic equilibrium 1 = 2. The rate constants have been measured for deprotonation of 1a-Br and 1b-Cl with 1,4-diazabicyclo[2,2,2]octane (DABCO) in solutions. UV, FTIR, H-1 and C-13 NMR spectra are consistent with the ylide structure of the deprotonated species. N-phenacyl-4-cyanopyridinium ylide (3a) is relatively stable in the solid state and unstable in solutions. The observed parallel changes in AS and the time of disappearance of the ylide absorption band suggest that solvation is responsible for the ylide stability. The UV-Vis spectra of 1a-Br and 1b-Cl with DABCO show solvent dependent isosbestic points, which suggest that-the decomposition reactions of ylides are very probably, uniform. The PM3 and B3LYP calculations were carried out to investigate the structures of the cations, ylides and their complexes with ammonia and DABCO. Ylides are formed by abstraction of hydroxy proton from cool form (2) via complex 8. (C) 2002 Elsevier Science B.V. All-rights reserved.

  DOI：

  10.1016/s0022-2860(02)00394-0

文献信息

• STEREOSELECTIVE HYDROALKYLIDENATION OF OLEFIN WITH PYRIDINIUM METHYLIDES
  作者：Otohiko Tsuge、Shuji Kanemasa、Shigeori Takenaka、Satoru Kuraoka

  DOI：10.1246/cl.1984.465

  日期：1984.3.5

  Acid-catalyzed elimination of pyridine from the stereoselective [3+2] cycloadducts between electron-deficient olefins and pyridinium methylides with ylide-stabilizing substituents offers a new type of C–C bond formation.

  从缺电子烯烃和具有叶立德稳定取代基的吡啶鎓甲基化物之间的立体选择性 [3+2] 环加合物中酸催化消除吡啶提供了一种新型的 C-C 键形成。