4,5-Dimethyl-4-hexen-1-yn-3-one | 103576-49-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,5-Dimethyl-4-hexen-1-yn-3-one
• 英文别名: 4,5-dimethyl-4-hexen-1-in-3-one；4,5-Dimethyl-4-hexen-1-in-3-on；4,5-dimethylhex-4-en-1-yn-3-one
• CAS: 103576-49-4
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: CAPGOOQSJSWHCT-UHFFFAOYSA-N

物化性质

• 沸点：
  173.5±23.0 °C(Predicted)
• 密度：
  0.906±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,5-Dimethyl-4-hexen-1-yn-3-one 在 天然维生素E 作用下， 以 various solvent(s) 为溶剂， 反应 12.0h， 以56%的产率得到2,3-二甲基-5-亚甲基-2-环戊烯-1-酮
  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：

  2,3-二甲基丁-2-烯酸 在 Sodium tetraborate decahydrate 、 氯化亚砜 作用下， 以 水 为溶剂， 反应 0.33h， 生成 4,5-Dimethyl-4-hexen-1-yn-3-one
  参考文献：
  名称：

  模具气相1-氟丁醚-1-异丁烯基-和2-甲基苯基-炔基-酮。Eine合成冯·埃诺霉素B †

  摘要：

  1-异丁烯基炔基和2-甲基苯基炔基酮的气流热解。甲基霉素B的合成

  DOI：

  10.1002/hlca.19860690306

文献信息

• The flow thermolyses of 1-isobutenyl alkynyl- and 2-methylphenyl alkynyl ketones. Synthesis of methylenomycin B
  作者：Manuel Roller、Martin Karpf、André S. Dreiding

  DOI：10.1016/s0040-4039(00)83928-3

  日期：1986.1

  lead to phenols and to cyclopentenones. The results are explained by a 5-ring carbene process (the known α-alkynone cyclization) and a 6-ring as well as a 5-ring addition process. The latter two (novel) processes are thought to be intramolecular “CH to CC additions” in two directions. The 5-ring addition process was used in a short (but low yield) synthesis of methylenomycin B.

  发现1-异丁烯基炔基和2-甲基苯基炔基酮的气流热解可导致苯酚和环戊烯酮。通过5-环卡宾法（已知的α-炔酮环化）和6-环以及5-环加成法解释了该结果。后两个（新的）过程被认为是两个方向上的分子内“CH至CC加成”。5环加成工艺用于甲基霉素（B）的短暂合成（但收率很低）。
• 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).
• 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.
• Die Gasphasen-Flussthermolyse von 1-Isobutenyl- und 2-Methylphenyl-alkinyl-ketonen. Eine Synthese von Methylenomycin B
  作者：Manuel Koller、Martin Karpf、Andr� S. Dreiding

  DOI：10.1002/hlca.19860690306

  日期：1986.5.7

  The Gas-Flow Thermolysis of 1-Isobutenyl Alkynyl and 2-Methylphenyl Alkynyl Ketones. Synthesis of Methylenomycin B

  1-异丁烯基炔基和2-甲基苯基炔基酮的气流热解。甲基霉素B的合成