endo-1,2-(dicarboxy-N-p-methylphenylimido)-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: endo-1,2-(dicarboxy-N-p-methylphenylimido)-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine
• 英文别名: (1R,12R,16S)-14-(4-methylphenyl)-13,15-dioxo-9,10,14-triazatetracyclo[8.6.0.02,7.012,16]hexadeca-2,4,6,8-tetraene-11,11-dicarbonitrile
• 化学式: C₂₂H₁₅N₅O₂
• 分子量: 381.393
• InChiKey: BDKKXTRSZMSLLG-FHWLQOOXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  29
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-(4-甲基苯基)-1H-吡咯-2,5-二酮 、 phthalazinium-2-dicyanomethanide 以 水 、 乙腈 为溶剂， 生成 endo-1,2-(dicarboxy-N-p-methylphenylimido)-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine
  参考文献：
  名称：

  Kinetic and synthetic influences of water and solvent-free conditions on 1,3-dipolar cycloaddition reactions: the phthalazinium and pyridazinium dicyanomethanide 1,3-dipoles: surprisingly successful synthetic methodsElectronic supplementary information (ESI) available: sample kinetic graphs and optimised transition state structures. See http://www.rsc.org/suppdata/p2/b2/b206028k/

  摘要：

  报道了水对 2-二氰基甲烷化 2-酞嗪 1 和二氰基甲烷化哒嗪 2 与各种亲偶极试剂的动力学和合成 1,3-偶极环加成反应的影响。水提高了所有反应的速率。嗜偶极细胞分为两组：正常水和超水。当溶剂从乙腈变为水时，前者表现出<20倍的速率增强，后者表现出>45倍的速率增强，但更常见的是数百倍。与烯烃或炔烃缀合的酮CO构成了水超亲偶极试剂。酯、醚、砜、腈和与烯烃共轭的芳环是水正常的亲偶极试剂。这些水效应的原因通过实验和高水平 DFT 进行了探索。疏水效应和特殊的氢键相互作用是涉及的主要因素。检查综合影响。尽管反应物不溶于水，但在水中和无溶剂条件下成功实现了高产率反应。

  DOI：

  10.1039/b206028k

文献信息

• Kinetic and synthetic influences of water and solvent-free conditions on 1,3-dipolar cycloaddition reactions: the phthalazinium and pyridazinium dicyanomethanide 1,3-dipoles: surprisingly successful synthetic methodsElectronic supplementary information (ESI) available: sample kinetic graphs and optimised transition state structures. See http://www.rsc.org/suppdata/p2/b2/b206028k/
  作者：Richard N. Butler、Anthony G. Coyne、William J. Cunningham、Luke A. Burke

  DOI：10.1039/b206028k

  日期：2002.10.30

  The influence of water on the kinetic and synthetic 1,3-dipolar cycloaddition reactions of phthalazinium-2-dicyanomethanide 1, and pyridazinium dicyanomethanide 2, with a wide range of dipolarophiles is reported. Water enhanced the rates of all reactions. The dipolarophiles were classified into two groups, water-normal and water-super. The former displayed rate enhancements of <20 times and the latter gave rate enhancements of >45 times, but more often some hundred times, on changing the solvent from acetonitrile to water. A ketone CO conjugated to an alkene or alkyne constitutes a water-super dipolarophile. Esters, ethers, sulfones, nitriles and aryl rings conjugated to an alkene are water-normal dipolarophiles. The causes of these water effects are explored experimentally and with high level DFT. Hydrophobic effects and special hydrogen bonding interactions are the main factors involved. Synthetic implications are examined. Despite insolubility of the reactants in water successful high-yield reactions were achieved in water and under solvent-free conditions.

  报道了水对 2-二氰基甲烷化 2-酞嗪 1 和二氰基甲烷化哒嗪 2 与各种亲偶极试剂的动力学和合成 1,3-偶极环加成反应的影响。水提高了所有反应的速率。嗜偶极细胞分为两组：正常水和超水。当溶剂从乙腈变为水时，前者表现出<20倍的速率增强，后者表现出>45倍的速率增强，但更常见的是数百倍。与烯烃或炔烃缀合的酮CO构成了水超亲偶极试剂。酯、醚、砜、腈和与烯烃共轭的芳环是水正常的亲偶极试剂。这些水效应的原因通过实验和高水平 DFT 进行了探索。疏水效应和特殊的氢键相互作用是涉及的主要因素。检查综合影响。尽管反应物不溶于水，但在水中和无溶剂条件下成功实现了高产率反应。