5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl | 143984-03-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl
• CAS: 143984-03-6
• 化学式: C₈H₁₄NO₂
• 分子量: 156.205
• InChiKey: ZAMUQQLKTFVPJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.81
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.54
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl 在 Tris buffer 作用下， 以 甲醇 为溶剂， 生成 bi(5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl)
  参考文献：
  名称：

  Equilibrium between 2-oxomorpholin-3-yl radicals and viologen radicals. Determination of reduction potentials

  摘要：

  Bi(3,5,5-trimethyl-2-oxomorpholin-3-yl) (TM-3 dimer) undergoes bond homolysis to yield 3,5,5-trimethyl-2-oxomorpholin-3-yl (TM-3), which reduces propyldiquat (PDQ2+) to its radical cation PDQ+. The byproduct is 5,6-dihydro-3, 5,5-trimethyl-1,4-oxazin-2-one (8). Similarly, bi(5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl) (DEM-3 dimer) cleaves to 5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl (DEM-3), which reduces paraquat (PQ2+) to its radical cation PQ+. The byproduct, 5,5-dimethyl-4-ethyl-3-methoxy-2-oxomorpholine (10), results from rapid addition of methanol solvent to the transient 5,6-dihydro-4-ethyl-5, 5-dimethyl-1,4-oxazin-2-onium cation (11). Concentration versus time data for the respective viologen radical cations together with reduction potentials for the viologens place the reduction potentials for TM-3 dimer and DEM-3 dimer at -0.56 and -0.33 V versus NHE, respectively, in Tris/Tris-H+ buffered methanol. The kinetics of reduction are analyzed using numerical integration, and the two reducing agents are compared with dithionite.

  DOI：

  10.1021/ja00027a026
• 作为产物：
  描述：

  bi(5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl) 在 Tris buffer 作用下， 以 甲醇 为溶剂， 生成 5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl
  参考文献：
  名称：

  Equilibrium between 2-oxomorpholin-3-yl radicals and viologen radicals. Determination of reduction potentials

  摘要：

  Bi(3,5,5-trimethyl-2-oxomorpholin-3-yl) (TM-3 dimer) undergoes bond homolysis to yield 3,5,5-trimethyl-2-oxomorpholin-3-yl (TM-3), which reduces propyldiquat (PDQ2+) to its radical cation PDQ+. The byproduct is 5,6-dihydro-3, 5,5-trimethyl-1,4-oxazin-2-one (8). Similarly, bi(5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl) (DEM-3 dimer) cleaves to 5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl (DEM-3), which reduces paraquat (PQ2+) to its radical cation PQ+. The byproduct, 5,5-dimethyl-4-ethyl-3-methoxy-2-oxomorpholine (10), results from rapid addition of methanol solvent to the transient 5,6-dihydro-4-ethyl-5, 5-dimethyl-1,4-oxazin-2-onium cation (11). Concentration versus time data for the respective viologen radical cations together with reduction potentials for the viologens place the reduction potentials for TM-3 dimer and DEM-3 dimer at -0.56 and -0.33 V versus NHE, respectively, in Tris/Tris-H+ buffered methanol. The kinetics of reduction are analyzed using numerical integration, and the two reducing agents are compared with dithionite.

  DOI：

  10.1021/ja00027a026

文献信息

• N-Alkyl-5,5-dimethyl-2-oxomorpholin-3-yl radicals. Characterization and reaction with molecular oxygen
  作者：Olester Benson、Samuel H. Demirdji、R. Curtis Haltiwanger、Tad H. Koch

  DOI：10.1021/ja00023a040

  日期：1991.11

  The synthesis of bi(4,5,5-trimethyl-2-oxomorpholin-3-yl) (TM-3' dimer), bi(5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl) (DEM-3 dimer), and bi(5,5-dimethyl-4-isopropyl-2-oxomorpholin-3-yl) (DIM-3 dimer) by one-electron oxidation of 4,5,5-trimethyl-2-oxomorpholine (8), 5,5-dimethyl-4-ethyl-2-oxomorpholine (9), and 5,5-dimethyl-4-isopropyl-2-oxomorpholine (10), respectively, with photochemically generated tert-butoxyl radical is described. dl-TM-3' dimer, meso-DEM-3 dimer, and meso-DIM-3 dimer were characterized from spectra and by X-ray crystallography. In solution the radical dimers existed in equilibrium with the captodatively substituted radicals, 4,5,5-trimethyl-2-oxomorpholin-3-yl (TM-3'), 5,5-dimethyl-4-ethyl-2-oxomorpholin-3-yl (DEM-3), and 5,5-dimethyl-4-isopropyl-2-oxomorpholin-3-yl (DIM-3), respectively, as indicated by EPR spectroscopy. The activation parameters for bond homolysis in ethanol solvent were measured by oxidatively trapping the radicals with diphenylpicrylhydrazyl (DPPH). The half-lives for bond homolysis vary by 5 orders of magnitude at 25-degrees-C with a value of only 2.3's for DIM-3 dimer. DIM-3 dimer reacted quantitatively with molecular oxygen to form a mixture of meso- and dl-bis(5,5-dimethyl-4-isopropyl-2-oxomorpholin-3-yl) peroxides (DIM-3 peroxides), which were isolated and characterized spectroscopically and analytically. At ambient temperature the peroxides fragmented by C-O bond homolysis to release the DIM-3 radical as indicated by EPR spectroscopy and were solvolyzed by protic solvent with release of hydrogen peroxide. The solvolysis was reversed by evaporation of the protic solvent, which restored most of the DIM-3 peroxides. The peroxides also slowly fragmented irreversibly to 5,5-dimethyl-3-hydroxy-4-isopropyl-2-oxomorpholine (21) and 5,5-dimethyl-2, 3-dioxo-4-isopropylmorpholine (23) in polar aprotic solvent.