endo-N-Methyl-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine-1,2-dicarboximide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: endo-N-Methyl-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine-1,2-dicarboximide
• 英文别名: endo-1,2-(dicarboxy-N-methylimido)-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine；(1R,12R,16S)-14-methyl-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: C₁₆H₁₁N₅O₂
• 分子量: 305.296
• InChiKey: RIKNETDBJNMBGM-AVGNSLFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  2,3-二氮杂萘 在 cesium fluoride 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 24.0h， 生成 endo-N-Methyl-3,3-dicyano-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine-1,2-dicarboximide
  参考文献：
  名称：

  Butler, Richard N.; Farrell, Derval M.; Pyne, Carmel S., Journal of Chemical Research - Part S, 1996, # 9, p. 418 - 419

  摘要：

  DOI：

文献信息

• Regioselectivity and endo/exo selectivity in the cycloadditions of the phthalazinium dicyanomethanide 1,3-dipole with unsymmetrical alkene and alkyne dipolarophiles. Unexpected reversals of regiochemistry: a combined experimental and DFT theoretical study
  作者：Richard N. Butler、Anthony G. Coyne、Patrick McArdle、Desmond Cunningham、Luke A. Burke

  DOI：10.1039/b101150m

  日期：——

  17. endo Cycloadditions were strongly favoured with alkene dipolarophiles containing π bonds in substituents on the alkene unit. With N-substituted maleimides endo products were formed exclusively even when the N-substituent was tBu or adamantyl. Only with alkoxyvinyl ethers were exo-cycloadducts encountered. The mechanisms are discussed in conjunction with DFT calculations. An X-ray crystal structure

  在反应 酞菁双氰胺 1,3-偶极电子贫乏的单取代 烯烃 和 炔烃双极性亲和剂双氰胺键合到未取代的碳上，得到1-取代的吡咯并[2,1- a ]酞嗪。对于富电子的双亲亲子体，其区域化学是相反的，并且产物是2-取代的吡咯并[2，1- a ]酞嗪。发生了区域化学的意外逆转甲基丙烯酸甲酯，由于C–Me组的空间效应，主要产品是 2-外-甲基-2-内-甲氧基羰基-3,3-二氰基-1,2,3,10b-四氢吡咯并[2,1- a ]酞嗪，17。内环加成受到强烈青睐烯烃在烯烃单元上的取代基中含有π键的亲二氟体。用N-取代马来酰亚胺 即使当N-取代基为t Bu或金刚烷基时，也仅形成内生产物。只有被烷氧乙烯基醚外-cycloadducts遇到。结合DFT计算讨论了这些机制。的X射线晶体结构报道于内切- ñ -叔丁基-3,3-二氰基1,2,3,10b四氢吡咯并[2,1-一个]酞嗪-1,2-二羧酰亚胺，25。
• 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。
• Steric Reversal of the endo-Selectivity Effect in 1,3-Dipolar Cycloadditions of Phthalazinium-2-ylides with N-Substituted Maleimides: endo- and exo-1,2-(Dicarboxy-N-substituted imido)-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazines†
  作者：Richard N. Butler、Derval M. Farrell

  DOI：10.1039/a708237a

  日期：——

  N-Methyl- and N-aryl-maleimides undergo cycloadditions with phthalazinium-2-dicyanomethanide and -2-unsubstituted methanide 1,3-dipoles to give exclusive or predominant endo-cycloadducts but with N-tert-butylmaleimide this endo effect is reversed to favour the exo-cycloadducts exo-1,2-(dicarboxy-N-tert-butylimido)-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazines 11 and 15.

  N-甲基-和N-芳基-马来酰亚胺与酞嗪鎓-2-二氰基甲基化物和-2-未取代的甲基化物1,3-偶极子发生环加成，产生排他性或主要的内环加合物，但与N-叔丁基马来酰亚胺相比，这种内切效应逆转为有利于外环加合物 exo-1,2-(二羧基-N-叔丁基亚氨基)-1,2,3,10b-四氢吡咯并[2,1-a]酞嗪 11 和 15。
• Water and Organic Synthesis: A Focus on the In-Water and On-Water Border. Reversal of the In-Water Breslow Hydrophobic Enhancement of the Normal <i>endo</i>-Effect on Crossing to On-Water Conditions for Huisgen Cycloadditions with Increasingly Insoluble Organic Liquid and Solid 2π-Dipolarophiles
  作者：Richard N. Butler、Anthony G. Coyne、William J. Cunningham、Eamon M. Moloney

  DOI：10.1021/jo400055g

  日期：2013.4.5

  Measurements of the endo/exo product ratios for Huisgen cycloadditions with a series of vinyl ketones, alkyl acrylates, and substituted styrenes as dipolarophiles with phthalazinium and pyridazinium dicyanomethanide 1,3-dipoles in acetonitrile and water show that as the reactions change from in-water (large hydrophobic enhancement of endo-products) to on-water, the hydrophobic enhancement of the endo-products is reduced and partially reversed (relative to acetonitrile). An expected increase of the endo-effect with increasing hydrophobic character of the dipolarophile is overcome by decreasing water solubility causing changeover to on-water conditions. On-water reactions do not show increased cycloaddition endo-effects (relative to organic solvents) as do in-water reactions.