Ethyl β-acetyl-α-cyano-α-methylisovalerate

• 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: Ethyl β-acetyl-α-cyano-α-methylisovalerate
• 英文别名: Ethyl 2-cyano-2,3,3-trimethyl-4-oxopentanoate
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: YPGNFPKIWHKYKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  67.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-溴-3-甲基-2-丁酮 、 2-氰基丙酸乙酯 在 potassium tert-butylate 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 5.0h， 以88%的产率得到Ethyl β-acetyl-α-cyano-α-methylisovalerate
  参考文献：
  名称：

  Alkylation of Nitrile Anions by Tertiary .alpha.-Halo Ketones and Nitriles

  摘要：

  Potassium salts of nitriles bearing carbethoxy, cyano, or phenyl groups at the alpha carbon [(RR'CCN)K:R' = CO(2)Et, CN, Ph] react with tertiary alpha-halo ketones and nitriles (1-5) in DMSO or HMPA to provide the alkylated beta-keto- or beta-cyano-beta,beta-dialkyl nitriles 6-10 in useful yields. (PhCHCN)(-) undergoes cyclization with p-XC(6)H(4)COCCl(CH3)(2) to produce 2(5H)-furanone 11. Reaction of (Ph(2)CCN)(-) with PhCOCCl(CH3)(2) affords the hydrolyzed ketone 12a and recovered carbon acid, while the anion undergoes oxidative dimerization to NCCPh(2)CPh(2)CN with p-O2NC6H4COCCl(CH3)(2) with concomitant formation of the reduced ketone p-O2NC6H4COCH(CH3)(2) and the hydrolyzed ketone 12b. The alkylations of [NCC(CH3)CO(2)Et](-) and [NCC(CH3)CN](-) with p-O(2)NC(6)H(4)COCX(CH3)(2) take place by the S(RN)1-process.

  DOI：

  10.1021/jo00122a018

文献信息

• Alkylation of Nitrile Anions by Tertiary .alpha.-Halo Ketones and Nitriles
  作者：Francisco Ros、Jose de la Rosa、Juan Enfedaque

  DOI：10.1021/jo00122a018

  日期：1995.9

  Potassium salts of nitriles bearing carbethoxy, cyano, or phenyl groups at the alpha carbon [(RR'CCN)K:R' = CO(2)Et, CN, Ph] react with tertiary alpha-halo ketones and nitriles (1-5) in DMSO or HMPA to provide the alkylated beta-keto- or beta-cyano-beta,beta-dialkyl nitriles 6-10 in useful yields. (PhCHCN)(-) undergoes cyclization with p-XC(6)H(4)COCCl(CH3)(2) to produce 2(5H)-furanone 11. Reaction of (Ph(2)CCN)(-) with PhCOCCl(CH3)(2) affords the hydrolyzed ketone 12a and recovered carbon acid, while the anion undergoes oxidative dimerization to NCCPh(2)CPh(2)CN with p-O2NC6H4COCCl(CH3)(2) with concomitant formation of the reduced ketone p-O2NC6H4COCH(CH3)(2) and the hydrolyzed ketone 12b. The alkylations of [NCC(CH3)CO(2)Et](-) and [NCC(CH3)CN](-) with p-O(2)NC(6)H(4)COCX(CH3)(2) take place by the S(RN)1-process.