mandelic acid-phenacyl ester | 117356-19-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: mandelic acid-phenacyl ester
• 英文别名: Inakt. α-Oxy-phenylessigsaeure-phenacylester；dl-Mandelsaeure-phenacetylester；Mandelsaeure-phenacylester；Phenacyl 2-hydroxy-2-phenylacetate；phenacyl 2-hydroxy-2-phenylacetate
• CAS: 117356-19-1
• 化学式: C₁₆H₁₄O₄
• 分子量: 270.285
• InChiKey: CYQUVNFDPSZFQL-UHFFFAOYSA-N

物化性质

• 熔点：
  78-80 °C
• 沸点：
  443.6±30.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  mandelic acid-phenacyl ester 在 N,N-二甲基苯胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以100%的产率得到扁桃酸
  参考文献：
  名称：

  Protecting Groups That Can Be Removed through Photochemical Electron Transfer:  Mechanistic and Product Studies on Photosensitized Release of Carboxylates from Phenacyl Esters

  摘要：

  Photolysis of electron-donating photosensitizers in the presence of various phenacyl esters (PhCOCH2-OCOR) results in C-O bond scission leading to the formation of acetophenone (PhCOCH3) and the corresponding carboxylic acid(RCO2H). Preparative experiments showed that the carboxylic acids are generated in high or quantitative isolated yields. It is argued that this reaction is initiated by a photoinduced electron transfer from the excited state sensitizer to the phenacyl ester. The latter process forms the anion radical of the phenacyl ester which in turn undergoes rapid C-O bond scission leading to the phenacyl radical and the corresponding carboxylate anion. This mechanism is supported by the following observations. (1) The phenacyl esters quench fluorescence from the sensitizers. (2) Analysis of the redox potentials of the sensitizer excited states and the substrates shows that the proposed electron transfer step is exergonic by 15-20 kcal/mol. (3) The byproducts are indicative of the proposed ion radical intermediates. In particular N-methylaniline is detected when N,N-dimethylaniline is used as a sensitizer. (4) Competing processes are observed in phenacyl esters whose acid components are themselves labile to single-electron transfer. For example, phenacyl 4-bromophenylacetate showed bromide elimination in competition with deprotection.

  DOI：

  10.1021/jo970495j
• 作为产物：
  描述：

  扁桃酸 、 2-溴苯乙酮 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 反应 2.0h， 以94%的产率得到mandelic acid-phenacyl ester
  参考文献：
  名称：

  Protecting Groups That Can Be Removed through Photochemical Electron Transfer:  Mechanistic and Product Studies on Photosensitized Release of Carboxylates from Phenacyl Esters

  摘要：

  Photolysis of electron-donating photosensitizers in the presence of various phenacyl esters (PhCOCH2-OCOR) results in C-O bond scission leading to the formation of acetophenone (PhCOCH3) and the corresponding carboxylic acid(RCO2H). Preparative experiments showed that the carboxylic acids are generated in high or quantitative isolated yields. It is argued that this reaction is initiated by a photoinduced electron transfer from the excited state sensitizer to the phenacyl ester. The latter process forms the anion radical of the phenacyl ester which in turn undergoes rapid C-O bond scission leading to the phenacyl radical and the corresponding carboxylate anion. This mechanism is supported by the following observations. (1) The phenacyl esters quench fluorescence from the sensitizers. (2) Analysis of the redox potentials of the sensitizer excited states and the substrates shows that the proposed electron transfer step is exergonic by 15-20 kcal/mol. (3) The byproducts are indicative of the proposed ion radical intermediates. In particular N-methylaniline is detected when N,N-dimethylaniline is used as a sensitizer. (4) Competing processes are observed in phenacyl esters whose acid components are themselves labile to single-electron transfer. For example, phenacyl 4-bromophenylacetate showed bromide elimination in competition with deprotection.

  DOI：

  10.1021/jo970495j

文献信息

• Rather; Reid, Journal of the American Chemical Society, 1919, vol. 41, p. 79
  作者：Rather、Reid

  DOI：——

  日期：——
• Protecting Groups That Can Be Removed through Photochemical Electron Transfer:  Mechanistic and Product Studies on Photosensitized Release of Carboxylates from Phenacyl Esters
  作者：Anamitro Banerjee、Daniel E. Falvey

  DOI：10.1021/jo970495j

  日期：1997.9.1

  Photolysis of electron-donating photosensitizers in the presence of various phenacyl esters (PhCOCH2-OCOR) results in C-O bond scission leading to the formation of acetophenone (PhCOCH3) and the corresponding carboxylic acid(RCO2H). Preparative experiments showed that the carboxylic acids are generated in high or quantitative isolated yields. It is argued that this reaction is initiated by a photoinduced electron transfer from the excited state sensitizer to the phenacyl ester. The latter process forms the anion radical of the phenacyl ester which in turn undergoes rapid C-O bond scission leading to the phenacyl radical and the corresponding carboxylate anion. This mechanism is supported by the following observations. (1) The phenacyl esters quench fluorescence from the sensitizers. (2) Analysis of the redox potentials of the sensitizer excited states and the substrates shows that the proposed electron transfer step is exergonic by 15-20 kcal/mol. (3) The byproducts are indicative of the proposed ion radical intermediates. In particular N-methylaniline is detected when N,N-dimethylaniline is used as a sensitizer. (4) Competing processes are observed in phenacyl esters whose acid components are themselves labile to single-electron transfer. For example, phenacyl 4-bromophenylacetate showed bromide elimination in competition with deprotection.