2-(1-Methylethylidene)-3-oxo-4-hexynenitrile | 141942-75-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(1-Methylethylidene)-3-oxo-4-hexynenitrile
• 英文别名: 3-Oxo-2-propan-2-ylidenehex-4-ynenitrile
• CAS: 141942-75-8
• 化学式: C₉H₉NO
• 分子量: 147.177
• InChiKey: USUMANFHFJFBJQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1-Methylethylidene)-3-oxo-4-hexynenitrile 在 天然维生素E 作用下， 以 various solvent(s) 为溶剂， 反应 12.0h， 以25%的产率得到4-ethylidene-2-methyl-5-oxocyclopentene-1-carbonitrile
  参考文献：
  名称：

  A convenient synthesis of methylenomycin B. Further mechanistic studies on the SET catalyzed electrocyclization of enynones.

  摘要：

  Methylenomycin B (3a) has been prepared in approximately 55% yield by SET catalyzed cyclization of enynone 1a. Mechanistic studies indicate that initial electron donation takes place at C-3 in enolized intermediates of type 2a.

  DOI：

  10.1016/s0040-4039(00)74185-2
• 作为产物：
  描述：

  3-Oxo-4-hexynenitrile 、 丙酮 在 吡啶 、 四氯化钛 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 以88%的产率得到2-(1-Methylethylidene)-3-oxo-4-hexynenitrile
  参考文献：
  名称：

  Enynones in Organic Synthesis. 7. Substituent Effects on the .alpha.-Tocopherol-Catalyzed Cyclization of Enynones to Methylenecyclopentenones. Convenient Syntheses of Members of the Methylenomycin Class of Antibiotics

  摘要：

  Substituent effects on the a-tocopherol (vitamin E, 3b) catalyzed cyclization of a wide variety of enynones 1a-z to methylenecyclopentenones 7a-z have been examined, with particular emphasis given to electron-withdrawing and -donating groups at positions 2-4 and 6. In general, electron-withdrawing groups at positions 4 and 6 dramatically accelerate the cyclization process, while strong electron-donating groups at positions 3 and 4 completely inhibit reaction. Relatively little effect is exerted by groups at C-2, except for the methyl ester derivative 1i, which is totally unreactive. This methodology was employed in the syntheses of the methylenecyclopentenone antibiotics methylenomycin B (7a) and desepoxy-4,5-didehydromethylenomycin A (7z) and in formal syntheses of methylenomycin A (8) and xanthocidin (9).

  DOI：

  10.1021/jo00097a036

文献信息

• A convenient synthesis of methylenomycin B. Further mechanistic studies on the SET catalyzed electrocyclization of enynones.
  作者：Peter A. Jacobi、Reginald O. Cann、David F. Skibbie

  DOI：10.1016/s0040-4039(00)74185-2

  日期：1992.4

  Methylenomycin B (3a) has been prepared in approximately 55% yield by SET catalyzed cyclization of enynone 1a. Mechanistic studies indicate that initial electron donation takes place at C-3 in enolized intermediates of type 2a.
• Enynones in Organic Synthesis. 7. Substituent Effects on the .alpha.-Tocopherol-Catalyzed Cyclization of Enynones to Methylenecyclopentenones. Convenient Syntheses of Members of the Methylenomycin Class of Antibiotics
  作者：Peter A. Jacobi、Harry L. Brielmann、Reginald O. Cann

  DOI：10.1021/jo00097a036

  日期：1994.9

  Substituent effects on the a-tocopherol (vitamin E, 3b) catalyzed cyclization of a wide variety of enynones 1a-z to methylenecyclopentenones 7a-z have been examined, with particular emphasis given to electron-withdrawing and -donating groups at positions 2-4 and 6. In general, electron-withdrawing groups at positions 4 and 6 dramatically accelerate the cyclization process, while strong electron-donating groups at positions 3 and 4 completely inhibit reaction. Relatively little effect is exerted by groups at C-2, except for the methyl ester derivative 1i, which is totally unreactive. This methodology was employed in the syntheses of the methylenecyclopentenone antibiotics methylenomycin B (7a) and desepoxy-4,5-didehydromethylenomycin A (7z) and in formal syntheses of methylenomycin A (8) and xanthocidin (9).