methyl 3-oxo-2-(4'-acetyl)phenylbutanoate | 172159-94-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-oxo-2-(4'-acetyl)phenylbutanoate
• CAS: 172159-94-3
• 化学式: C₁₃H₁₄O₄
• 分子量: 234.252
• InChiKey: LUWJGILLQJCMCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.73
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  60.44
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl 3-oxo-2-(4'-acetyl)phenylbutanoate 在 potassium tert-butylate 、 碘 、 氧气 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以8%的产率得到methyl 2-hydroxy-3-oxo-2-(4'-acetyl)phenylbutanoate
  参考文献：
  名称：

  A study on the mechanism and scope of the radical-mediated oxidation of arylacetoacetates

  摘要：

  Arylacetoacetate 1a undergoes an oxidative degradation in the presence of K(t)BuO, THF, catalytic I-2 and O-2, to give keto ester 4 as major compound. Hydrolysis and decarboxylation of this intermediate led to the corresponding arylcarboxylic acid 3a in satisfactory overall yields. By experiments conducted in the presence of O-18(2), incorporation of atmosphere oxygen into the benzylic position of 4 was evidenced. Furthermore, spin-trap experiments showed that benzyl radical 7 was generated in the reaction medium, which supports its role as intermediate in the pathway leading to the observed oxidation products. A plausible mechanism for this process is presented. On the other hand, appropriate conditions for achieving the alkylation of these arylacetoacetates with no concomitant formation of oxidation side-products are reported. Finally, arylacetates suffer also this degradative oxidation process leading to the corresponding arylcarboxylic acids without isolation of the intermediate keto ester derivative.

  DOI：

  10.1016/0040-4020(95)00576-t
• 作为产物：
  描述：

  乙酰乙酸甲酯 钠盐 、 methyl 4-<(tert-butylthio)diazenyl>phenyl ketone 以 二甲基亚砜 为溶剂， 反应 10.0h， 以50%的产率得到methyl 3-oxo-2-(4'-acetyl)phenylbutanoate
  参考文献：
  名称：

  A study on the mechanism and scope of the radical-mediated oxidation of arylacetoacetates

  摘要：

  Arylacetoacetate 1a undergoes an oxidative degradation in the presence of K(t)BuO, THF, catalytic I-2 and O-2, to give keto ester 4 as major compound. Hydrolysis and decarboxylation of this intermediate led to the corresponding arylcarboxylic acid 3a in satisfactory overall yields. By experiments conducted in the presence of O-18(2), incorporation of atmosphere oxygen into the benzylic position of 4 was evidenced. Furthermore, spin-trap experiments showed that benzyl radical 7 was generated in the reaction medium, which supports its role as intermediate in the pathway leading to the observed oxidation products. A plausible mechanism for this process is presented. On the other hand, appropriate conditions for achieving the alkylation of these arylacetoacetates with no concomitant formation of oxidation side-products are reported. Finally, arylacetates suffer also this degradative oxidation process leading to the corresponding arylcarboxylic acids without isolation of the intermediate keto ester derivative.

  DOI：

  10.1016/0040-4020(95)00576-t