2-phthalyl-4-pentenenitrile

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 2-phthalyl-4-pentenenitrile
• 英文别名: 2-(1,3-Dioxoisoindol-2-yl)pent-4-enenitrile
• 化学式: C₁₃H₁₀N₂O₂
• 分子量: 226.235
• InChiKey: ZACJOFQYBBPDRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  61.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  邻苯二甲酰甘氨酸 在 bromotriphenylphosphonium bromide 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 生成 2-phthalyl-4-pentenenitrile
  参考文献：
  名称：

  Rearrangements of Substituted 3-Aza-1,2,5-hexatrienes. 3. The Scope and Versatility of an Extremely Mild 3-Aza-Cope Reaction

  摘要：

  An investigation of the [3,3]-sigmatropic reaction of substituted 3-aza-1,2,5-hexatrienes to give 4-pentenenitriles is presented. This reaction has been found to occur under a wide variety of reactions conditions (10 are reported) starting from readily available N-allylamides. In contrast to other 3-aza-Cope reactions, this process occurs at room temperature, under essentially neutral conditions, allowing for the facile preparation of substituted nitrile products in moderate to excellent yields. The scope and versatility of this reaction are demonstrated by its use on a wide variety of substrates, including nitrogen- and oxygen-substituted amides. The rearrangements of cis- and trans-4-tert-butyl-N-allylcyclohexanecarboxamides 16a and 16b are reported and were found to give a ratio of axial to equatorial (A:E) products consistent with A:E ratios found for other related sigmatropic reactions. The stereochemical requirements for this reaction appear to be similar to other [3,3]-rearrangements even though the transition state for this rearrangement is most likely neither boat nor chairlike.

  DOI：

  10.1021/jo951587g

文献信息

• An extremely mild 3-aza-claisen reaction. 2. New conditions and the rearrangement of α-heteroatom substituted amides
  作者：M.A. Walters、A.B. Hoem、H.R. Arcand、A.D. Hegeman、C.S. McDonough

  DOI：10.1016/s0040-4039(00)60316-7

  日期：1993.2

  Several new and potentially useful reaction conditions for the 3-aza-Claisen rearrangement of N-allyl amides have been developed. These new conditions have been successfully applied to the rearrangement of α-heteroatom substituted species forming α-amino nitriles and protected cyanohydrins as products.

  已经开发出几种新的和潜在有用的N-烯丙基酰胺的3-氮杂-克莱森重排反应条件。这些新条件已成功地应用于形成α-氨基腈和受保护的氰醇的α-杂原子取代物种的重排。
• Rearrangements of Substituted 3-Aza-1,2,5-hexatrienes. 3. The Scope and Versatility of an Extremely Mild 3-Aza-Cope Reaction
  作者：Michael A. Walters、Andrew B. Hoem、Colleen S. McDonough

  DOI：10.1021/jo951587g

  日期：1996.1.1

  An investigation of the [3,3]-sigmatropic reaction of substituted 3-aza-1,2,5-hexatrienes to give 4-pentenenitriles is presented. This reaction has been found to occur under a wide variety of reactions conditions (10 are reported) starting from readily available N-allylamides. In contrast to other 3-aza-Cope reactions, this process occurs at room temperature, under essentially neutral conditions, allowing for the facile preparation of substituted nitrile products in moderate to excellent yields. The scope and versatility of this reaction are demonstrated by its use on a wide variety of substrates, including nitrogen- and oxygen-substituted amides. The rearrangements of cis- and trans-4-tert-butyl-N-allylcyclohexanecarboxamides 16a and 16b are reported and were found to give a ratio of axial to equatorial (A:E) products consistent with A:E ratios found for other related sigmatropic reactions. The stereochemical requirements for this reaction appear to be similar to other [3,3]-rearrangements even though the transition state for this rearrangement is most likely neither boat nor chairlike.