Methyl 4,4-dimethyl-2,3-dioxopentanoate | 136201-83-7

• 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: Methyl 4,4-dimethyl-2,3-dioxopentanoate
• CAS: 136201-83-7
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: QHMIMOIPHYJSDE-UHFFFAOYSA-N

物化性质

• 沸点：
  225.9±23.0 °C(Predicted)
• 密度：
  1.087±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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 4,4-dimethyl-2,3-dioxopentanoate 在 air 作用下， 生成 Methyl 4,4-dimethyl-3-oxo-2,2-dihydroxypentanoate
  参考文献：
  名称：

  Synthesis of .alpha.-diketones by direct, low-temperature, in situ nucleophilic acylation of esters by acyllithium reagents

  摘要：

  Addition of n-, sec-, or tert-butyllithium to a CO-saturated solution of an ester, R'CO2R'' in a solvent system of 4:4:1 (by volume) THF/Et2O/pentane at -110-degrees-C (or at -135-degrees-C in 3:1 (by volume) Me2O/THF), followed by hydrolysis with saturated aqueous NH4Cl, results in the formation of alpha-diketones, BuC(O)C(O)R', yellow liquids, in good yield. Similar reactions with diethyl succinate gave in one instance both t-BuC(O)C(O)CH2CH2CO2Et and t-BuC(O)C(O)CH2CH2C(O)C(O)Bu-t. The monoacylation product of dimethyl oxalate, t-BuC(O)C(O)CO2Me, readily formed a crystalline hydrate, t-BuC(O)C(OH)2CO2Me.

  DOI：

  10.1021/jo00020a014
• 作为产物：
  描述：

  methyl 2-hydroxy-4,4-dimethyl-3-oxopentanoate 在 copper diacetate 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 Methyl 4,4-dimethyl-2,3-dioxopentanoate 、 Methyl 4,4-dimethyl-3-oxo-2,2-dihydroxypentanoate
  参考文献：
  名称：

  Metal-Free α-Hydroxylation of α-Unsubstituted β-Oxoesters and β-Oxoamides

  摘要：

  A direct metal-free a-hydroxylation of a-unsubstituted beta-oxoesters and beta-oxoamides was developed using m-chloroperbenzoic acid as the oxidant. This transformation enabled straightforward metal-free access to important a-hydroxy-beta-dicarbonyl moieties under mild reaction conditions. Furthermore, the hydroxylated products were readily converted into vicinal tricarbonyl compounds, which are useful synthetic precursors of numerous biological targets.

  DOI：

  10.1021/jo501985u

文献信息

• Direct Synthesis of <i>N</i> -Acyl-<i>N</i> ,<i>O</i> -hemiacetals <i>via</i> Nucleophilic Addition of Unactivated Amides and Their <i>O</i> -Acetylation: Access to α,α-Difunctionalized <i>N</i> -Acylimines
  作者：Haruyasu Asahara、Kanami Inoue、Shinki Tani、Kazuto Umezu、Nagatoshi Nishiwaki

  DOI：10.1002/adsc.201600436

  日期：2016.9.1

  metal‐free synthesis of polyfunctionalized N‐acyl‐N,O‐hemiacetals was developed via the nucleophilic addition of unactivated amides to ketones. The protocol demonstrated a wide substrate scope, with good isolated yields. Additionally, their O‐acetylated products serve as a precursor of α,α‐difunctionalized N‐acylimines. An addition reaction of broad scope of nucleophiles to generate N‐acylimines is

  通过未活化酰胺的亲核加成反应，开发了一种温和，无金属的多官能团N-酰基N，O-半缩醛合成方法。该方案证明了广泛的底物范围，具有良好的分离产率。此外，它们的O乙酰化产物可作为α，α-双官能化N-酰亚胺的前体。还报道了广泛范围的亲核试剂加成反应，生成N-嘧啶。