Acetic acid 1-(2-hydroxy-5-oxo-2,5-dihydro-furan-3-yl)-undeca-2,6-diynyl ester | 136617-58-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Acetic acid 1-(2-hydroxy-5-oxo-2,5-dihydro-furan-3-yl)-undeca-2,6-diynyl ester
• 英文别名: 1-(2-hydroxy-5-oxo-2H-furan-3-yl)undeca-2,6-diynyl acetate
• CAS: 136617-58-8
• 化学式: C₁₇H₂₀O₅
• 分子量: 304.343
• InChiKey: FYXOKXNJPIQXIM-UHFFFAOYSA-N

物化性质

• 沸点：
  512.8±50.0 °C(Predicted)
• 密度：
  1.208±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-(trimethylsilyl)-4-furaldehyde 在 rose bengal 氧气 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 Acetic acid 1-(2-hydroxy-5-oxo-2,5-dihydro-furan-3-yl)-undeca-2,6-diynyl ester
  参考文献：
  名称：

  Singlet oxygen oxidation of substituted furans to 5-hydroxy-2(5H)-furanone

  摘要：

  The conditions for the regiospecific singlet oxygen oxidation of various 2,4-disubstituted furans 9 to 4-substituted-2 (5H)-furanones 3 are developed. The presence of a C-2 substituent (e.g., trimethylsilyl, tert-butyldimethylsilyl, or tributylstannyl) in 9 is an absolute requirement for the formation of the 4-substituted-5-hydroxy-2(5H)-furanone regioisomer 3. When the C-2 substituent is triethylsilyl (TES) or TBDMS, however, apart from 3, the corresponding 5-trialkylsiloxy derivative 11 is also isolated in a significant amount. These silyl acetals are unexpectedly stable but can be hydrolyzed back to 3 on stirring with dilute acid. The formation of silyl acetals, to our knowledge, has never been reported in the singlet oxygen oxidation of (trialkylsilyl)furan. A plausible mechanism for their formation is proposed. The presence of a catalytic amount of water in the oxidation of 2-(trialkylsilyl)-4-substituted-furans not only eliminates the formation of the silyl acetals but also speeds up the rate of the oxidation process. Moreover, the oxidation can then be carried out at 0-degrees-C instead of at -78-degrees-C. Oxidation of 2-(1-hydroxyalkyl)-4-substituted-furans in the absence of a reducing agent gives little or no sign of 2,5-disubstituted-6-hydroxy-3(2H)-pyranone 23 but instead 26 selectively. Thus, the (1-hydroxy)alkyl group can be utilized as the trialkylsilyl or trialkylstannyl group in dictating the regioselectivity in the singlet oxygen oxidation of substituted furans.

  DOI：

  10.1021/jo00025a012

文献信息

• Anti-inflammatory furanones
  申请人：ALLERGAN, INC

  公开号：EP0295056B1

  公开（公告）日：1992-08-05
• US5134128A
  申请人：——

  公开号：US5134128A

  公开（公告）日：1992-07-28
• Singlet oxygen oxidation of substituted furans to 5-hydroxy-2(5H)-furanone
  作者：Gary C. M. Lee、Elizabeth T. Syage、Dale A. Harcourt、Judy M. Holmes、Michael E. Garst

  DOI：10.1021/jo00025a012

  日期：1991.12

  The conditions for the regiospecific singlet oxygen oxidation of various 2,4-disubstituted furans 9 to 4-substituted-2 (5H)-furanones 3 are developed. The presence of a C-2 substituent (e.g., trimethylsilyl, tert-butyldimethylsilyl, or tributylstannyl) in 9 is an absolute requirement for the formation of the 4-substituted-5-hydroxy-2(5H)-furanone regioisomer 3. When the C-2 substituent is triethylsilyl (TES) or TBDMS, however, apart from 3, the corresponding 5-trialkylsiloxy derivative 11 is also isolated in a significant amount. These silyl acetals are unexpectedly stable but can be hydrolyzed back to 3 on stirring with dilute acid. The formation of silyl acetals, to our knowledge, has never been reported in the singlet oxygen oxidation of (trialkylsilyl)furan. A plausible mechanism for their formation is proposed. The presence of a catalytic amount of water in the oxidation of 2-(trialkylsilyl)-4-substituted-furans not only eliminates the formation of the silyl acetals but also speeds up the rate of the oxidation process. Moreover, the oxidation can then be carried out at 0-degrees-C instead of at -78-degrees-C. Oxidation of 2-(1-hydroxyalkyl)-4-substituted-furans in the absence of a reducing agent gives little or no sign of 2,5-disubstituted-6-hydroxy-3(2H)-pyranone 23 but instead 26 selectively. Thus, the (1-hydroxy)alkyl group can be utilized as the trialkylsilyl or trialkylstannyl group in dictating the regioselectivity in the singlet oxygen oxidation of substituted furans.