6-tert-butyl-3-isopropyl-2-(phenylimino)-5-pivaloyl-1,3-oxazin-4-one | 144542-95-0

• 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-(phenylimino)-5-pivaloyl-1,3-oxazin-4-one
• 英文别名: 6-Tert-butyl-5-(2,2-dimethylpropanoyl)-2-phenylimino-3-propan-2-yl-1,3-oxazin-4-one
• CAS: 144542-95-0
• 化学式: C₂₂H₃₀N₂O₃
• 分子量: 370.492
• InChiKey: ZEXZEUDLUVNGBX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  dipivaloylketene 、 6-tert-butyl-3-isopropyl-2-(phenylimino)-5-pivaloyl-1,3-oxazin-4-one 以 正己烷 为溶剂， 以92%的产率得到2,8-di-tert-butyl-5-isopropyl-11-phenyl-3,9-dipivaloyl-1,7-dioxa-5,11-diazaspiro<5.5>undeca-2,8-diene-4,10-dione
  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
• 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 2.0h， 生成 6-tert-butyl-3-isopropyl-2-(phenylimino)-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