3-Oxo-4-hexynoic acid ethyl ester | 50496-37-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 3-Oxo-4-hexynoic acid ethyl ester
• 英文别名: Ethyl-3-oxo-hexynoat；3-Oxo-4-hexinsaeureaethylester；4-Hexynoic acid, 3-oxo-, ethyl ester；ethyl 3-oxohex-4-ynoate
• CAS: 50496-37-2
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: MBFMOTRQABWXHL-UHFFFAOYSA-N

物化性质

• 沸点：
  226.8±42.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Oxo-4-hexynoic acid ethyl ester 、 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35%的产率得到2-(1-Methylethylidene)-3-oxo-4-hexynoic acid ethyl ester
  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
• 作为产物：
  描述：

  2-丁炔酸乙酯 、 乙酸乙酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以70%的产率得到3-Oxo-4-hexynoic acid ethyl ester
  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 alkylated 4-hydroxy-2-pyrones
  作者：Eiji Suzuki、Haruo Sekizaki、Shoji Inoue

  DOI：10.1039/c39730000568

  日期：——

  Various alkylated 4-hydroxy-2-pyrones were synthesized from the βδ-diketo-esters (11), (13), and (14), which were easily prepared from the γδ-acetylenic β-keto-esters(3), (4), and (7)via the corresponding enamino-β-keto-esters (8)–(10).

  各种烷基化的4-羟基-2-吡喃酮从合成的β δ二酮-酯（11），（13）和（14），它很容易从制备的γ δ炔属β酮酯（3） ，（4）和（7）经由相应的烯氨基-β-酮酸酯（8）–（10）。
• 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.
• SUZUKI E.; SEKIZAKI H.; INOUE S., J. CHEM. RES. SYNOP., 1977, NO 8, 200
  作者：SUZUKI E.、 SEKIZAKI H.、 INOUE S.

  DOI：——

  日期：——
• 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).