meso-bi(4,5,5-trimethyl-2-oxomorpholin-3-yl) | 136476-51-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: meso-bi(4,5,5-trimethyl-2-oxomorpholin-3-yl)
• CAS: 136476-51-2
• 化学式: C₁₄H₂₄N₂O₄
• 分子量: 284.356
• InChiKey: ZILNLKKERXBEIT-AOOOYVTPSA-N

反应信息

• 作为产物：
  描述：

  3,3,4,8,8,9-hexamethyloctahydro-4H,9H<1,4>dioxano<2,3-b:5,6-b'>bis<1,4>oxazine 在 二叔丁基过氧化物 作用下， 以 叔丁醇 为溶剂， 175.0 ℃ 、101.33 kPa 条件下， 反应 24.0h， 生成 meso-bi(4,5,5-trimethyl-2-oxomorpholin-3-yl)
  参考文献：
  名称：

  N-Alkyl-5,5-dimethyl-2-oxomorpholin-3-yl radicals. Characterization and reaction with molecular oxygen

  摘要：

  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.

  DOI：

  10.1021/ja00023a040