2-acetyl-2-methyl-4-oxo-pentanoic acid ethyl ester | 111400-47-6

• 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: 2-acetyl-2-methyl-4-oxo-pentanoic acid ethyl ester
• 英文别名: ethyl 2-acetyl-2-methyl-4-oxopentanoate；2-acetyl-2-methyl-4-oxo-valeric acid ethyl ester；2-Acetyl-2-methyl-4-oxo-valeriansaeure-aethylester
• CAS: 111400-47-6
• 化学式: C₁₀H₁₆O₄
• 分子量: 200.235
• InChiKey: NVOHXJVCGHWXNV-UHFFFAOYSA-N

物化性质

• 沸点：
  120-121 °C(Press: 10 Torr)
• 密度：
  1.046±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  2-acetyl-2-methyl-4-oxo-pentanoic acid ethyl ester 生成 2,3,5-三甲基-4-吡咯羧酸乙酯 、 2,3,5-Trimethyl-pyrrole-1-carboxylic acid ethyl ester
  参考文献：
  名称：

  Thermal rearrangement of 3H-pyrroles by competitive [1,5]-sigmatropic shifts, and the reversibility of the 3H- to 2H-pyrrole interconversion

  摘要：

  DOI：

  10.1016/s0040-4039(00)96207-5
• 作为产物：
  描述：

  乙酰乙酸乙酯 在 sodium hydride 、 potassium carbonate 、 potassium iodide 作用下， 以 丙酮 为溶剂， 反应 66.0h， 生成 2-acetyl-2-methyl-4-oxo-pentanoic acid ethyl ester
  参考文献：
  名称：

  吡咯烷的合成与化学。第18部分。通过paal-knorr反应制备3-乙氧基羰基-3h-吡咯，以及涉及竞争性酯迁移至c-2，c-4和n的σ重排。

  摘要：

  3H-吡咯-3-羧酸酯（4）在某些情况下与具有外环双键的异构体（5）和（6）一起通过适当取代的2-乙氧基羰基-1,4-二酮（1）的环化反应制备用液氨，然后在沸腾溶剂中用铝矾土将可分离的2-羟基-3,4-二氢-2H-吡咯中间体（2）和（3）脱水。在甲苯或对二甲苯中长时间加热会通过竞争性的[1,5]σ重排将3H吡咯（4）定量转化为1H-吡咯的异构体4酯（11）和N-酯（13）。在相同条件下，将可分离的中间体2H-吡咯-2-羧酸酯（l2）类似地转化为相同的产物。

  DOI：

  10.1016/s0040-4020(01)81514-3

文献信息

• Manganese(III) Acetate-mediated Alkylation of 1,3-Dicarbonyls to Form Tricarbonyl Compounds Bearing a Quaternary Carbon Centre
  作者：Gregory Bar、Andrew F. Parsons、C. Barry Thomas

  DOI：10.1055/s-2002-32576

  日期：——

  1,3-Dicarbonyl compounds including ethyl 2-methylacetoacetate can be efficiently alkylated with enol ethers or enol esters in the presence of manganese(III) acetate. These intermolecular radical addition reactions can be used to form sterically congested quaternary carbon centres in excellent yield (81-97%).

  在乙酸锰 (III) 存在下，包括 2-甲基乙酰乙酸乙酯在内的 1,3-二羰基化合物可以用烯醇醚或烯醇酯有效地烷基化。这些分子间自由基加成反应可用于以优异的产率 (81-97%) 形成空间拥挤的季碳中心。
• Manganese(iii) acetate-mediated alkylation of β-keto esters and β-keto amides: an enantio- and diastereo-selective approach to substituted pyrrolidinones
  作者：Gregory Bar、Andrew F. Parsons、C. Barry Thomas

  DOI：10.1039/b209123b

  日期：2003.1.13

  beta-Keto esters and beta-keto amides can be efficiently alkylated on reaction with enol ethers and manganese(III) acetate in the presence of copper(II) acetate. These intermolecular radical addition reactions can be used to construct quaternary carbon centres in excellent yield and this method has been utilised in a diastereoselective approach to substituted pyrrolidinones.

  在乙酸铜（II）的存在下，与烯醇醚和乙酸锰（III）反应，可以有效地将β-酮酯和β-酮酰胺烷基化。这些分子间自由基加成反应可用于以优异的产率构建季碳中心，并且该方法已经以非对映选择性的方式用于取代的吡咯烷酮。
• Novel One-Pot Vicinal Double C-Acylation of Styrenes and Methacrylates by Electroreduction
  作者：Yoshimasa Yamamoto、Hirofumi Maekawa、Satoshi Goda、Ikuzo Nishiguchi

  DOI：10.1021/ol035020v

  日期：2003.7.1

  Electroreduction of styrenes or alkyl methacrylates in the presence of aliphatic acid anhydrides or N-acylinnidazoles with an undivided cell equipped with zinc electrodes as the anode and the cathode brought about novel one-pot vicinal double C-acylation to afford the corresponding 1,4-diketones in satisfactory yields.
• Control of the regioselectivity of oxidative free-radical cyclizations by addition to haloalkenes
  作者：Barry B. Snider、Qingwei Zhang、Mark A. Dombroski

  DOI：10.1021/jo00041a026

  日期：1992.7

  Chlorine substituents on the alkene control the regioselectivity of the cyclization of 5-hexenyl or 6-heptenyl radicals generated by oxidation of an acetoacetate ester or 1,3-diketone with Mn(OAc)3.2H2O. 6-Exo-cyclization of the radicals obtained by oxidation of benzoylacetone derivatives 10 and 13, containing a chlorine on the terminal double bond carbon, gives alpha-chloroalkyl radicals that add to the aromatic ring to give 11 and 16, respectively. Loss of HCl leads to naphthols 8 and 17 indicating that this reaction may be useful for aureolic acid synthesis. Exo-cyclization is the exclusive process with acetoacetates 28b, 44, 55b, and 59 containing a chlorine on the terminal double bond carbon. 6-Endo-cyclization is the exclusive process with acetoacetates 18c and 51b containing a chlorine on the internal double bond carbon. Intra- and intermolecular competition experiments indicate that these effects are primarily steric. The chlorine substituent controls the regioselectivity of the cyclization by sterically hindering attack of the radical on the chlorine bearing double bond carbon thereby retarding formation of the beta-chloroalkyl radical. The chlorine substituent does not electronically accelerate attack on the other end of the double bond to give the alpha-chloroalkyl radical.
• Goldberg; Mueller, Helvetica Chimica Acta, 1938, vol. 21, p. 1701
  作者：Goldberg、Mueller

  DOI：——

  日期：——