(E)-ethyl 3-(pyren-4-yl)acrylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: (E)-ethyl 3-(pyren-4-yl)acrylate
• 英文别名: (E)-ethyl-3-(pyren-4-yl)acrylate；ethyl (E)-3-pyren-4-ylprop-2-enoate
• 化学式: C₂₁H₁₆O₂
• 分子量: 300.357
• InChiKey: LLUMEBYBDHWOSF-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-溴芘 、 丙烯酸乙酯 在 palladium diacetate 、 potassium carbonate 、 三(邻甲基苯基)磷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以65%的产率得到(E)-ethyl 3-(pyren-4-yl)acrylate
  参考文献：
  名称：

  Aerobic Palladium(II)-Catalyzed Dehydrogenative Heck Reaction in the Synthesis of Pyrenyl Fluorophores. A Photophysical Study of β-Pyrenyl Acrylates in Solution and in the Solid State

  摘要：

  An aerobic dehydrogenative Heck reaction of pyrene (1a) and 2,7-di-tert-butylpyrene (1b) with ethyl acrylate is reported. The reaction is catalyzed by a Pd(OAc)2/4,5-diazafluoren-9-one (DAF) system and takes place in acetic or pivalic acid as solvents at 110-130 degrees C. The reaction of 1a afforded a 6:1 mixture of C-1- and C-4-alkenylated pyrenes (2a and 3a, respectively) in 71% yield. In the case of 1b, only a C-4-substituted product (3b) was formed in 46% yield. Compounds 2a and 3a,b exhibited fluorescence in solution and in the solid state. In chloroform and THF solution the fluorescence maxima were in the range of 440-465 nm, and quantum yields decreased in the order 2a > 3a> 3b. In the solid state, 3a,b showed blue-green fluorescence (Phi(F) = 0.26 and 0.14, respectively), whereas 2a emitted yellow-green fluorescence) (Phi(F) = 0.35). Besides blue-emitting monomers, the presence of green-emitting aggregated species (preformed dimers) in the crystals of 3a,b and red-emitting dynamic excimers in the crystals of 2a has been demonstrated. Single-crystal X-ray diffraction analyses of 2a and 3b confirmed pi-stacking of pyrenyl moieties in the crystals of the former and the absence of stacking in the crystals of the latter compound.

  DOI：

  10.1021/jo502619k

文献信息

• Aerobic Palladium(II)-Catalyzed Dehydrogenative Heck Reaction in the Synthesis of Pyrenyl Fluorophores. A Photophysical Study of β-Pyrenyl Acrylates in Solution and in the Solid State
  作者：Michał Piotrowicz、Janusz Zakrzewski、Rémi Métivier、Arnaud Brosseau、Anna Makal、Krzysztof Woźniak

  DOI：10.1021/jo502619k

  日期：2015.3.6

  An aerobic dehydrogenative Heck reaction of pyrene (1a) and 2,7-di-tert-butylpyrene (1b) with ethyl acrylate is reported. The reaction is catalyzed by a Pd(OAc)2/4,5-diazafluoren-9-one (DAF) system and takes place in acetic or pivalic acid as solvents at 110-130 degrees C. The reaction of 1a afforded a 6:1 mixture of C-1- and C-4-alkenylated pyrenes (2a and 3a, respectively) in 71% yield. In the case of 1b, only a C-4-substituted product (3b) was formed in 46% yield. Compounds 2a and 3a,b exhibited fluorescence in solution and in the solid state. In chloroform and THF solution the fluorescence maxima were in the range of 440-465 nm, and quantum yields decreased in the order 2a > 3a> 3b. In the solid state, 3a,b showed blue-green fluorescence (Phi(F) = 0.26 and 0.14, respectively), whereas 2a emitted yellow-green fluorescence) (Phi(F) = 0.35). Besides blue-emitting monomers, the presence of green-emitting aggregated species (preformed dimers) in the crystals of 3a,b and red-emitting dynamic excimers in the crystals of 2a has been demonstrated. Single-crystal X-ray diffraction analyses of 2a and 3b confirmed pi-stacking of pyrenyl moieties in the crystals of the former and the absence of stacking in the crystals of the latter compound.