3-acetyl-2-methyl-4-oxo-valeric acid ethyl ester | 32702-14-0

• 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: 3-acetyl-2-methyl-4-oxo-valeric acid ethyl ester
• 英文别名: 3-Acetyl-2-methyl-4-oxo-valeriansaeure-aethylester；Ethyl 3-acetyl-2-methyl-4-oxopentanoate
• CAS: 32702-14-0
• 化学式: C₁₀H₁₆O₄
• 分子量: 200.235
• InChiKey: GJAKVEZXDGDNIS-UHFFFAOYSA-N

物化性质

• 沸点：
  295.7±20.0 °C(Predicted)
• 密度：
  1.042±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 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：

  3-acetyl-2-methyl-4-oxo-valeric acid ethyl ester 在 乙醚 、 硫酸 、 氨 作用下， 生成 1-(5-acetoxy-2,4-dimethyl-pyrrol-3-yl)-ethanone
  参考文献：
  名称：

  Fischer; Adler, Hoppe-Seyler's Zeitschrift fur Physiologische Chemie, 1931, vol. 197, p. 237,245, 278

  摘要：

  DOI：
• 作为产物：
  描述：

  乙酰丙酮 、 2-溴丙酸乙酯 在 P(MeNCH₂CH₂)3N 作用下， 以 正己烷 、 乙腈 为溶剂， 反应 0.5h， 以95%的产率得到3-acetyl-2-methyl-4-oxo-valeric acid ethyl ester
  参考文献：
  名称：

  Use of the Nonionic Superbase P(MeNCH₂CH₂)₃N in the Selective Monoalkylation of Active-Methylene Compounds

  摘要：

  The symmetric active-methylene compounds CH2(CO2Et)(2) and CH2[C(O)Me](2) are selectively monoalkylated in the presence of 1.1 equiv of a variety of alkyl halides and 1 equiv of the nonionic superbase P(MeNCH2CH2)(3)N in 85-98% yields in 30 min at room temperature. The unsymmetrical active-methylene compound EtO2CCH2C(O)Me is selectively monoalkylated under the same conditions, except for the temperature, which is 0 degrees C, in 59-88% yields. The observation of selective C-rather than O-alkylation is rationalized in terms of the formation of an enolate whose negatively charged oxygen is sterically protected by a nearby HP(MeNCH2CH2)(3)N+ counterion in a tight ion pair.

  DOI：

  10.1021/jo972350i

文献信息

• March, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1902, vol. 134, p. 180
  作者：March

  DOI：——

  日期：——
• US4146721A
  申请人：——

  公开号：US4146721A

  公开（公告）日：1979-03-27
• US4325962A
  申请人：——

  公开号：US4325962A

  公开（公告）日：1982-04-20
• Fischer; Adler, Hoppe-Seyler's Zeitschrift fur Physiologische Chemie, 1931, vol. 197, p. 237,245, 278
  作者：Fischer、Adler

  DOI：——

  日期：——
• Use of the Nonionic Superbase P(MeNCH₂CH₂)₃N in the Selective Monoalkylation of Active-Methylene Compounds
  作者：Subramaniam Arumugam、Dale McLeod、John G. Verkade

  DOI：10.1021/jo972350i

  日期：1998.5.1

  The symmetric active-methylene compounds CH2(CO2Et)(2) and CH2[C(O)Me](2) are selectively monoalkylated in the presence of 1.1 equiv of a variety of alkyl halides and 1 equiv of the nonionic superbase P(MeNCH2CH2)(3)N in 85-98% yields in 30 min at room temperature. The unsymmetrical active-methylene compound EtO2CCH2C(O)Me is selectively monoalkylated under the same conditions, except for the temperature, which is 0 degrees C, in 59-88% yields. The observation of selective C-rather than O-alkylation is rationalized in terms of the formation of an enolate whose negatively charged oxygen is sterically protected by a nearby HP(MeNCH2CH2)(3)N+ counterion in a tight ion pair.