1-phenyl-3-(pyren-1-yl)urea | 1430335-58-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 1-phenyl-3-(pyren-1-yl)urea
• 英文别名: 1-Phenyl-3-pyren-1-ylurea；1-phenyl-3-pyren-1-ylurea
• CAS: 1430335-58-2
• 化学式: C₂₃H₁₆N₂O
• 分子量: 336.393
• InChiKey: OYLZKPIMRCOENM-UHFFFAOYSA-N

物化性质

• 沸点：
  475.4±14.0 °C(Predicted)
• 密度：
  1.387±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.1
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-phenyl-3-(pyren-1-yl)urea 、 四丁基氟化铵 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  The Interaction of Fluoride with Fluorogenic Ureas: An ON¹–OFF–ON² Response

  摘要：

  The anion binding tendencies of the two fluorogenic ureas (LH)-H-1 and (LH)-H-2, containing the 2-anthracenyl and 1-pyrenyl moieties as signaling units, respectively, have been investigated in MeCN and DMSO by absorption, emission, and H-1 NMR spectroscopies. The formation of stable 1:1 receptor:anion H-bond complexes has been confirmed by structural studies on the crystalline [Bu4N]-[L-1 center dot center dot center dot Cl] and [Bu4N][(LH)-H-2 center dot center dot center dot CH3COO] salts. Complexation induces significant variations of the emission properties of (LH)-H-1 and L2H according to a multifaceted behavior, which depends upon the fluorogenic substituent, the solvent, and the basicity of the anion. Poorly basic anions (Cl-, Br-) cause a red shift of the emission band(s). Carboxylates (CH3COO-, C6H5COO-) induce fluorescence quenching due to the occurrence of an electrontransfer process taking place in the locally excited complex [*L-H center dot center dot center dot X](-). However, this excited complex may undergo an intracomplex proton transfer from one urea N-H fragment to the anion, to give the tautomeric excited complex [L center dot center dot center dot H-X](-)*, which emits at higher wavelength. F- displays a unique behavior: It forms with (LH)-H-1 a stable [L-H...F]- complex which in the excited state undergoes intracomplex proton transfer, to give the poorly emissive excited tautomer [L center dot center dot center dot H-F](-)*. With (LH)-H-2, on moderate addition of F-, the 1:1 H-bond complex forms, and the blue fluorescence of pyrene is quenched. Large excess addition of F- promotes deprotonation of the ground state complex, according to the equilibrium [(LH)-H-2 center dot center dot center dot F](-) + F- reversible arrow HF2-. The deprotonated receptor [L-2](-) is distinctly emissive (yellow fluorescence), which generates the fluorimetric response ON1-OFF-ON2 of receptor (LH)-H-2 with respect to F-.

  DOI：

  10.1021/ja4019786
• 作为产物：
  描述：

  1-氨基芘 、 异氰酸苯酯 以 四氢呋喃 为溶剂， 反应 23.0h， 以70%的产率得到1-phenyl-3-(pyren-1-yl)urea
  参考文献：
  名称：

  Aggregated Excimer Formation through Hydrogen Bonding in a Pyrene–Urea Derivative

  摘要：

  我们研究了带有脲单元的芘衍生物的分子间氢键相互作用，称为 1PUP（一个芘基）和 1DPU（两个芘基）。 1DPU 显示出约 530 nm 的新发射带以及归因于芘部分的局部激发发射 (LE)，即使在 10−7 M 处，与仅具有 LE 的 1PUP 相比，表明对称配置允许稳定堆叠1DPU。时间分辨发射光谱表明，随着 1DPU 浓度的增加，新谱带的强度相对于 LE 的强度有所增加。此外，由于与 1DPU 形成氢键，添加乙酸四丁基铵 (TBAAc) 导致新带消失。这些结果表明，即使在非常低的浓度下，新谱带也可能源自 1DPU 分子之间通过尿素单元的分子间氢键相互作用，并且可归因于准分子发射。这意味着1DPU的脲单元形成的氢键有利于在没有阴离子的情况下形成准分子的构象，并且1DPU分子之间的氢键相互作用的强度弱于1DPU分子之间的相互作用和阴离子。

  DOI：

  10.1246/bcsj.20150060

文献信息

• The Interaction of Fluoride with Fluorogenic Ureas: An ON¹–OFF–ON² Response
  作者：Valeria Amendola、Greta Bergamaschi、Massimo Boiocchi、Luigi Fabbrizzi、Lorenzo Mosca

  DOI：10.1021/ja4019786

  日期：2013.4.24

  The anion binding tendencies of the two fluorogenic ureas (LH)-H-1 and (LH)-H-2, containing the 2-anthracenyl and 1-pyrenyl moieties as signaling units, respectively, have been investigated in MeCN and DMSO by absorption, emission, and H-1 NMR spectroscopies. The formation of stable 1:1 receptor:anion H-bond complexes has been confirmed by structural studies on the crystalline [Bu4N]-[L-1 center dot center dot center dot Cl] and [Bu4N][(LH)-H-2 center dot center dot center dot CH3COO] salts. Complexation induces significant variations of the emission properties of (LH)-H-1 and L2H according to a multifaceted behavior, which depends upon the fluorogenic substituent, the solvent, and the basicity of the anion. Poorly basic anions (Cl-, Br-) cause a red shift of the emission band(s). Carboxylates (CH3COO-, C6H5COO-) induce fluorescence quenching due to the occurrence of an electrontransfer process taking place in the locally excited complex [*L-H center dot center dot center dot X](-). However, this excited complex may undergo an intracomplex proton transfer from one urea N-H fragment to the anion, to give the tautomeric excited complex [L center dot center dot center dot H-X](-)*, which emits at higher wavelength. F- displays a unique behavior: It forms with (LH)-H-1 a stable [L-H...F]- complex which in the excited state undergoes intracomplex proton transfer, to give the poorly emissive excited tautomer [L center dot center dot center dot H-F](-)*. With (LH)-H-2, on moderate addition of F-, the 1:1 H-bond complex forms, and the blue fluorescence of pyrene is quenched. Large excess addition of F- promotes deprotonation of the ground state complex, according to the equilibrium [(LH)-H-2 center dot center dot center dot F](-) + F- reversible arrow HF2-. The deprotonated receptor [L-2](-) is distinctly emissive (yellow fluorescence), which generates the fluorimetric response ON1-OFF-ON2 of receptor (LH)-H-2 with respect to F-.
• Aggregated Excimer Formation through Hydrogen Bonding in a Pyrene–Urea Derivative
  作者：Hisato Matsumoto、Yoshinobu Nishimura、Tatsuo Arai

  DOI：10.1246/bcsj.20150060

  日期：2015.8.15

  We examined intermolecular hydrogen-bonding interactions of pyrene derivatives bearing a urea unit, referred to as 1PUP (one pyrenyl group) and 1DPU (two pyrenyl groups). 1DPU showed a new emission band around 530 nm along with a locally excited emission (LE) attributed to the pyrene moiety, even at 10−7 M, in contrast to 1PUP, which only had an LE, indicating that the symmetrical configuration allowed stable stacking of 1DPU. Time-resolved emission spectroscopy revealed that the intensity of the new band increased relative to that of the LE with the concentration of 1DPU. Furthermore, addition of tetrabutylammonium acetate (TBAAc) resulted in the disappearance of the new band, due to the formation of hydrogen bonds with 1DPU. These results indicate that the new band may originate from intermolecular hydrogen-bonding interactions between 1DPU molecules through the urea unit, even at very low concentrations, and can be attributed to an excimer emission. This implies that hydrogen bond formation by the urea units of 1DPU favors a conformation that results in the formation of the excimer in the absence of anions, and the strength of the hydrogen-bonding interaction between 1DPU molecules is weaker than the interaction between a 1DPU molecule and an anion.

  我们研究了带有脲单元的芘衍生物的分子间氢键相互作用，称为 1PUP（一个芘基）和 1DPU（两个芘基）。 1DPU 显示出约 530 nm 的新发射带以及归因于芘部分的局部激发发射 (LE)，即使在 10−7 M 处，与仅具有 LE 的 1PUP 相比，表明对称配置允许稳定堆叠1DPU。时间分辨发射光谱表明，随着 1DPU 浓度的增加，新谱带的强度相对于 LE 的强度有所增加。此外，由于与 1DPU 形成氢键，添加乙酸四丁基铵 (TBAAc) 导致新带消失。这些结果表明，即使在非常低的浓度下，新谱带也可能源自 1DPU 分子之间通过尿素单元的分子间氢键相互作用，并且可归因于准分子发射。这意味着1DPU的脲单元形成的氢键有利于在没有阴离子的情况下形成准分子的构象，并且1DPU分子之间的氢键相互作用的强度弱于1DPU分子之间的相互作用和阴离子。