3-(chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one | 135005-70-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪类
• 英文名称: 3-(chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one
• 英文别名: 3-(chloromethyl)-5,5-dimethyl-5,6-dihydro-1,4-oxazin-2-one；3-(Chloromethyl)-5,5-dimethyl-5,6-dihydro-2H-1,4-oxazin-2-one；5-(chloromethyl)-3,3-dimethyl-2H-1,4-oxazin-6-one
• CAS: 135005-70-8
• 化学式: C₇H₁₀ClNO₂
• 分子量: 175.615
• InChiKey: AWUGZJGBKPFZCW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  ——	5,6-dihydro-3,5,5-trimethyl-1,4-oxazin-2-one	53153-46-1	C7H11NO2	141.17

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	3-(acetoxymethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one	86527-99-3	C9H13NO4	199.207

反应信息

• 作为反应物：
  描述：

  3-(chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.02h， 生成 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a-hexahydro-9,9a-(1'-phenyl-2',5'-dioxo-1',3',4'-triazoline-3',4'-diyl)-4,4,8,8-tetramethylanthracene-1,5,-dione
  参考文献：
  名称：

  Synthesis, structure, and reactivity of an antiaromatic, 2,5-dicarboxy-stabilized 1,4-dihydropyrazine

  摘要：

  3-(Chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one (4) undergoes self-condensation in the presence of diisopropylethylamine to yield 4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione (DDTTA). DDTTA is an example of a modestly stable, almost flat 1,4-dihydropyrazine. It is green in color, and the long-wavelength visible absorption band shows significant solvatochromism. DDTTA gives reversible one-electron-oxidation waves in methylene chloride at -0.33 and 0.61 V vs ferrocene/ferrocenium (0.07 and 1.01 V vs NHE, respectively) and reacts with Fe(1,10-phenanthroline)3(3+) to yield DDT7A+ (5) characterized by ESR spectroscopy. The radical cation is also produced in purple-black crystals by cocrystallization with tetracyanoquinodimethane (TCNQ). The black material has the composition DDTTA+-TCNQ)2-, and in solution it is unstable to molecular oxygen. Air-stable radical cation 5 is produced by air oxidation of DDTTA in trifluoroacetic acid. The resulting trifluoroacetate crystallizes as pale blue parallelepipeds with the composition DDTTA+CF3CO2-(CF3CO2H)2; the radical cations are arranged in sheets with short C-H...O intermolecular contacts as established by X-ray analysis. DDTTA reacts with molecular oxygen in acetic acid to yield the unstable dioxetane 7, 4a,8a-diaza-2,6-dioxa-9,9a-epidioxy-3,4,7,8,9,9a-hexahydro-4,4,8,8-tetramethylanthracene-1,5-dione, and in acetonitrile to yield the aldehyde 9, 5,6-dihydro-2-oxo-5,5-dimethyl-1,4-oxazine-3-carboxaldehyde. Mechanisms for the air oxidations are proposed in Scheme I. [2 + 21-Cycloaddition of DDTTA occurs with 1-phenyl-1,3,4-triazoline-2,5-dione (PTAD) to give the diazetidine 17. Catalytic hydrogenation of DDTTA gives 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a-hexahydro-4,4,8,8-tetramethylanthracene-1,5-dione (13), which air oxidizes to a mixture of DDTTA and 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a-hexahydro-9a-hydroxy-4,4,8,8-tetramethylanthracene-1,5-dione (14) via the relatively persistent, purple radical cation 16. DDTTA represents a new electron donor with three stable redox states and, consequently, has potential as a component in formation of organic electrically conducting materials.

  DOI：

  10.1021/ja00041a018
• 作为产物：
  描述：

  5,6-dihydro-3,5,5-trimethyl-1,4-oxazin-2-one 在 次氯酸叔丁酯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 3-(chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one
  参考文献：
  名称：

  Substituent effects on the formation of aminocarboxy-type capto-dative free radicals

  摘要：

  DOI：

  10.1021/jo00166a010