6-tert-butyl-3-isopropyl-2-(isopropylimino)-5-pivaloyl-1,3-oxazin-4-one | 144542-91-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-tert-butyl-3-isopropyl-2-(isopropylimino)-5-pivaloyl-1,3-oxazin-4-one
• 英文别名: 6-Tert-butyl-5-(2,2-dimethylpropanoyl)-3-propan-2-yl-2-propan-2-ylimino-1,3-oxazin-4-one
• CAS: 144542-91-6
• 化学式: C₁₉H₃₂N₂O₃
• 分子量: 336.475
• InChiKey: PGICCVUGZXDEDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  59
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6-tert-butyl-3-isopropyl-2-(isopropylimino)-5-pivaloyl-1,3-oxazin-4-one 在 盐酸 作用下， 反应 0.25h， 以67%的产率得到6-tert-butyl-3-isopropyl-5-pivaloyl-1,3-oxazine-2,4-dione
  参考文献：
  名称：

  [2+4] Cycloaddition reactions of neat dipivaloylketene

  摘要：

  DOI：

  10.1007/bf00810021
• 作为产物：
  描述：

  5-tert-butyl-4-pivaloyl-2,3-dihydrofuran-2,3-dione 以 正己烷 为溶剂， 25.0~400.0 ℃ 、1.33 Pa 条件下， 反应 1.0h， 生成 6-tert-butyl-3-isopropyl-2-(isopropylimino)-5-pivaloyl-1,3-oxazin-4-one
  参考文献：
  名称：

  Dipivaloylketene and its dimers. [2+4] Versus [2+2] cycloaddition reactions of .alpha.-oxo ketenes

  摘要：

  Dipivaloylketene (8) is generated by preparative flash vacuum pyrolysis of furandione 6. While dimerization of 8 in apolar and several polar solvents leads to the previously reported [2 + 4] dimer 7, dimerization in the presence of DMSO, tributylphosphine oxide, or pyridine instead surprisingly occurs across the C=O bond of the ketene function, affording dioxinone 9. This is a novel type of alpha-oxo ketene dimerization. The reversibility of both dimerizations and mechanistic pathways for the formation of 9 are discussed. Cycloaddition reactions of 8 with heterocumulenes 10a,b and 12a-c yield [2 + 4] cycloadducts 11a,b and 13a-c, respectively. Oxazinones 13a-c can add a second molecule of 8 to generate novel spiro heterocycles 14a-c. In contrast, oxo ketene 7 reacts with carbodiimides 12a,b, to furnish [2 + 2] adducts 15a,b. This is the first unequivocal example of a direct [2 + 2] cycloaddition reaction of an alpha-oxo ketene. The unexpected formation of these compounds was confirmed by X-ray crystallography (15a). General aspects of [2 + 2] versus [2 + 4] cycloaddition in alpha-oxo ketenes are discussed.

  DOI：

  10.1021/jo00052a018

文献信息

• [2+4] Cycloaddition reactions of neat dipivaloylketene
  作者：C. Oliver Kappe、Curt Wentrup、Gert Kollenz

  DOI：10.1007/bf00810021

  日期：1993.11
• Dipivaloylketene and its dimers. [2+4] Versus [2+2] cycloaddition reactions of .alpha.-oxo ketenes
  作者：C. Oliver Kappe、Gerald Faerber、Curt Wentrup、Gert Kollenz

  DOI：10.1021/jo00052a018

  日期：1992.12

  Dipivaloylketene (8) is generated by preparative flash vacuum pyrolysis of furandione 6. While dimerization of 8 in apolar and several polar solvents leads to the previously reported [2 + 4] dimer 7, dimerization in the presence of DMSO, tributylphosphine oxide, or pyridine instead surprisingly occurs across the C=O bond of the ketene function, affording dioxinone 9. This is a novel type of alpha-oxo ketene dimerization. The reversibility of both dimerizations and mechanistic pathways for the formation of 9 are discussed. Cycloaddition reactions of 8 with heterocumulenes 10a,b and 12a-c yield [2 + 4] cycloadducts 11a,b and 13a-c, respectively. Oxazinones 13a-c can add a second molecule of 8 to generate novel spiro heterocycles 14a-c. In contrast, oxo ketene 7 reacts with carbodiimides 12a,b, to furnish [2 + 2] adducts 15a,b. This is the first unequivocal example of a direct [2 + 2] cycloaddition reaction of an alpha-oxo ketene. The unexpected formation of these compounds was confirmed by X-ray crystallography (15a). General aspects of [2 + 2] versus [2 + 4] cycloaddition in alpha-oxo ketenes are discussed.