diethyl α-acetoxy-α-methylmalonate | 122086-24-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl α-acetoxy-α-methylmalonate
• 英文别名: diethyl α-(acetoxymethyl)malonate；Diethyl 2-(acetyloxy)-2-methylmalonate；diethyl 2-acetyloxy-2-methylpropanedioate
• CAS: 122086-24-2
• 化学式: C₁₀H₁₆O₆
• 分子量: 232.233
• InChiKey: WEDRSFVMDKQFSU-UHFFFAOYSA-N

物化性质

• 沸点：
  283.9±20.0 °C(Predicted)
• 密度：
  1.137±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  乙酸酐 、 甲基丙二酸二乙酯 在 iron(III) perchlorate 作用下， 以60%的产率得到diethyl α-acetoxy-α-methylmalonate
  参考文献：
  名称：

  Fe（III）盐对羰基化合物的氧化脱质子作用

  摘要：

  乙腈或乙酸酐中的铁（III）盐（高氯酸盐和硝酸盐九水合物）在0–50°C下可通过相应的自由基有效氧化丙二酸酯的α-位。在烯烃和芳族化合物的存在下，观察到分子间和分子内的自由基链或氧化加成。

  DOI：

  10.1016/s0040-4039(00)72739-0

文献信息

• Synthesis of substituted tetrahydronaphthalenes by manganese(III), cerium(IV), and iron(III) oxidation of substituted diethyl .alpha.-benzylmalonates in the presence of olefins
  作者：Attilio Citterio、Roberto Sebastiano、Antonio Marion、Roberto Santi

  DOI：10.1021/jo00018a023

  日期：1991.8

  The oxidation of substituted diethyl alpha-benzylmalonates (1a-m) by manganese(III) acetate in acetic acid, cerium(IV) ammonium nitrate in methanol, or iron(III) perchlorate in acetonitrile in the presence of substituted olefins 2a-u was investigated. The results are consistent with a common mechanism. It involves selective generation of malonyl radicals from high-valent metal malonyl complexes, their addition to the olefin, and competition of the adduct radical between intramolecular cyclization to produce highly functionalized tetrahydronaphthalenes (3) and oxidation by metal salt to give mainly gamma-lactones (5). Several electron-withdrawing and releasing substituents on the aromatic ring and on the olefin can be successfully used in the synthesis of 3 without olefin telomerization. The influence of metal and olefin or aromatic substituents on the homolytic addition and intramolecular aromatic substitution is discussed.
• Oxidation of malonic acid derivatives by manganese(III) acetate. Aromatic malonylation reaction. Scope and limitations
  作者：Attilio Citterio、Roberto Santi、Tiziana Fiorani、Sauro Strologo

  DOI：10.1021/jo00272a046

  日期：1989.5
• CITTERIO, ATTILIO;SANTI, ROBERTO;FIORANI, TIZIANA;STROLOGO, SAURO, J. ORG. CHEM., 54,(1989) N1, C. 2703-2712
  作者：CITTERIO, ATTILIO、SANTI, ROBERTO、FIORANI, TIZIANA、STROLOGO, SAURO

  DOI：——

  日期：——
• Oxidative deprotonation of carbonyl compounds by Fe(III) salts
  作者：Attilio Citterio、Anna Cerati、Roberto Sebastiano、Claudia Finzi、Roberto Santi

  DOI：10.1016/s0040-4039(00)72739-0

  日期：1989.1

  Iron (III) salts (perchlorate and nitrate nonahydrate) in acetonitrile or acetic anhydride at 0–50°C oxidize the ∝-position of malonic esters efficiently via the corresponding radicals. In the presence of olefins and aromatics, inter- and intramolecular free radical chain or oxidative additions are observed.

  乙腈或乙酸酐中的铁（III）盐（高氯酸盐和硝酸盐九水合物）在0–50°C下可通过相应的自由基有效氧化丙二酸酯的α-位。在烯烃和芳族化合物的存在下，观察到分子间和分子内的自由基链或氧化加成。