methyl 3-oxo-2-(4'-isobutyryl)phenylbutanoate | 172159-87-4

• 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'-isobutyryl)phenylbutanoate
• 英文别名: Methyl 2-[4-(2-methylpropanoyl)phenyl]-3-oxobutanoate
• CAS: 172159-87-4
• 化学式: C₁₅H₁₈O₄
• 分子量: 262.306
• InChiKey: VYTALXNIJXEOCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3-oxo-2-(4'-isobutyryl)phenylbutanoate 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 25.0 ℃ 、392.24 kPa 条件下， 反应 9.0h， 以82%的产率得到methyl 3-oxo-2-(4'-isobutyl)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：

  1-(4-氨基苯基)-2-甲基丙烷-1-酮 在 盐酸 、 sodium hydroxide 、 potassium tert-butylate 、 sodium nitrite 作用下， 以 二甲基亚砜 为溶剂， 生成 methyl 3-oxo-2-(4'-isobutyryl)phenylbutanoate
  参考文献：
  名称：

  芳基偶氮硫化物光诱导β-二羰基化合物芳基化及其在甲基标记的2-芳基丙酸合成中的比较研究

  摘要：

  提出了一种通过光诱导分解芳基偶氮硫化物使β-二羰基衍生物（乙酰丙酮，乙酰乙酸甲酯和丙二酸二甲酯）芳基化的比较研究。所使用的芳基偶氮硫化物包含与酮洛芬或布洛芬有关的芳基部分，并且该反应按照Dell'Erba等人的报告的方法进行。（四面体，1991，47，333）。从所分析的芳基偶氮硫化物，仅那些带有与苯环连接的羰基的那些，即1和11，以令人满意的产率提供了相应的芳基化加合物。关于β-二羰基衍生物，在1的情况下乙酰丙酮的缩合。丙二酸二甲酯中11的结果最好。然而，对于2-芳基丙二酸酯衍生物的情况，芳基β-二羰基加合物的进一步甲基化显然是有利的。使用该合成策略方便地制备在C-2处的甲基标记的酮洛芬（23％的总产率，3-硝基二苯甲酮7步）和布洛芬（34％的总产率，4异丁酰苯8步）异位异构体也有报道。

  DOI：

  10.1016/s0040-4020(01)85294-7

文献信息

• Tona Merce, Sanchez-Baeza Francisco, Messeguer Angel, Tetrahedron, 50 (1994) N 27, S 8117-8126
  作者：Tona Merce, Sanchez-Baeza Francisco, Messeguer Angel

  DOI：——

  日期：——
• A study on the mechanism and scope of the radical-mediated oxidation of arylacetoacetates
  作者：Mercè Tona、Marisa Guardiola、Lluis Fajarí、Angel Messeguer

  DOI：10.1016/0040-4020(95)00576-t

  日期：1995.1

  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.
• A comparative study on the photo-induced arylation of β-dicarbonyl compounds by arylazosulfides and its use in the synthesis of methyl labeled 2-arylpropionic acids
  作者：Mercè Tona、Francisco Sánchez-Baeza、Angel Messeguer

  DOI：10.1016/s0040-4020(01)85294-7

  日期：1994.1

  corresponding arylation adducts in satisfactory yields. Concerning the β-dicarbonyl derivatives, condensation of acetylacetone in the case of 1 and of dimethyl malonate in that of 11 gave the best results. However, the further methylation of the aryl β-dicarbonyl adduct was clearly advantageous for the case of the 2-arylmalonate derivatives. The use of this synthetic strategy for the convenient preparation of

  提出了一种通过光诱导分解芳基偶氮硫化物使β-二羰基衍生物（乙酰丙酮，乙酰乙酸甲酯和丙二酸二甲酯）芳基化的比较研究。所使用的芳基偶氮硫化物包含与酮洛芬或布洛芬有关的芳基部分，并且该反应按照Dell'Erba等人的报告的方法进行。（四面体，1991，47，333）。从所分析的芳基偶氮硫化物，仅那些带有与苯环连接的羰基的那些，即1和11，以令人满意的产率提供了相应的芳基化加合物。关于β-二羰基衍生物，在1的情况下乙酰丙酮的缩合。丙二酸二甲酯中11的结果最好。然而，对于2-芳基丙二酸酯衍生物的情况，芳基β-二羰基加合物的进一步甲基化显然是有利的。使用该合成策略方便地制备在C-2处的甲基标记的酮洛芬（23％的总产率，3-硝基二苯甲酮7步）和布洛芬（34％的总产率，4异丁酰苯8步）异位异构体也有报道。