1-anthracen-2-yl-3-phenylurea | 1313507-89-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1-anthracen-2-yl-3-phenylurea
• 英文别名: 3-(anthracen-2-yl)-1-phenylurea；anthracen-2-yl-3-phenylurea；1-(Anthracen-2-yl)-3-phenylurea
• CAS: 1313507-89-9
• 化学式: C₂₁H₁₆N₂O
• 分子量: 312.371
• InChiKey: OMZACCARMQKRNV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• 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-anthracen-2-yl-3-phenylurea 、 四丁基氟化铵 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：

  2-氨基蒽 、 异氰酸苯酯 以 四氢呋喃 为溶剂， 反应 22.0h， 以61.1%的产率得到1-anthracen-2-yl-3-phenylurea
  参考文献：
  名称：

  Kinetics of Hydrogen Bonding between Anthracene Urea Derivatives and Anions in the Excited State

  摘要：

  Urea compounds are useful anion sensors due to their hydrogen-bonding capabilities. We investigated the emissive properties of complexes consisting of urea anthracene (nPUA, n = 1, 2) host compounds and acetate anions held as guests through intermolecular hydrogen bonding. The kinetics of a new emission band formed by conformational changes in the excited singlet state were revealed. The new band is thought to arise from a charge-transfer interaction between the anthracene and urea moieties after intermolecular hydrogen-bond reconfiguration in the excited state, with rate constants of 2.4 x 10(9) and 4.0 x 10(7) s(-1) for 1PUA and 2PUA, respectively.

  DOI：

  10.1021/jp2022693

文献信息

• Effect of Moderate Hydrogen Bonding on Tautomer Formation via Excited-State Intermolecular Proton-Transfer Reactions in an Aromatic Urea Compound with a Steric Base
  作者：Kei Togasaki、Tatsuo Arai、Yoshinobu Nishimura

  DOI：10.1021/acs.jpca.0c05045

  日期：2020.8.20

  using time-resolved fluorescence measurement. Based on the association constants in the ground state, the intermolecular hydrogen bond between 2PUA and DBU was less stable than the bond between 2PUA and Ac due to steric hindrance and the geometry of the hydrogen bond. In the fluorescence spectra, 2PUA–DBU displayed prominent tautomeric emission in chloroform (CHCl3), whereas 2PUA–Ac exhibited distinct

  1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）尽管结构受阻仍具有较高的碱性，但仍形成弱氢键，被用于研究通过激发态分子间质子转移（ESPT）形成互变异构体）反应。使用时间分辨荧光测量，将在DBU存在下蒽-2-基-3-苯基脲（2PUA）的ESPT反应动力学与乙酸根阴离子（Ac）的动力学进行了比较。基于基态的缔合常数，由于空间位阻和氢键的几何形状，2PUA和DBU之间的分子间氢键比2PUA和Ac之间的分子间氢键不稳定。在荧光光谱中，2PUA–DBU在氯仿（CHCl 3），而2PUA–Ac在二甲基亚砜（DMSO）中表现出明显的互变异构排放。动力学分析表明，当溶剂的质子接受能力提高时，2PUA–DBU的ESPT反应速率常数显着降低，而2PUA–Ac的反应则与溶剂极性而不是质子接受能力有关。这些结果表明，由于位阻而产生的适度氢键受存在的溶剂类型的影响，特别是如果溶剂表现出像DMSO那样的质子
• Kinetic analysis of photoinduced reactions in hydrogen-bonded complexes of anthracene-urea with anions
  作者：Haruki Masai、Satomi Ikedu、Yoshinobu Nishimura、Tatsuo Arai

  DOI：10.1016/j.jphotochem.2012.09.011

  日期：2012.12

  assign the transient species as X, which is the ground state responsible for longer wavelength emissions, and conclude that the dissipation of the transient species corresponded to recovery of the complex in the ground state. We propose a reaction scheme for the photochemical process applying to urea derivatives in the presence of anions.

  在乙酸根阴离子（乙酸四丁基铵，TBAAc）存在下，尿素-蒽类n PUA（n  = 1，2，9 ; PUA = 1-蒽-n-基-3-苯基脲）的瞬态吸收测量得到寿命约为100μs的瞬态物质，不受O 2的影响。寿命显示出显着的温度依赖性，这使我们能够确定ΔH ‡和ΔS ‡。Δ小号‡有较大的负值，相反，Δ ħ ‡，表明过渡形式的耗散过程是熵控制。之间的线性关系Ť ΔS ‡和ΔH ‡提出了熵-焓补偿，通常在具有氢键的宿主-客体系统中发现。这些发现使我们可以将瞬态物种指定为X，这是负责更长波长发射的基态，并得出结论，瞬态物种的耗散与基态中复合物的恢复相对应。我们提出了一种在阴离子存在下应用于脲衍生物的光化学过程的反应方案。
• Kinetics of Hydrogen Bonding between Anthracene Urea Derivatives and Anions in the Excited State
  作者：Satomi Ikedu、Yoshinobu Nishimura、Tatsuo Arai

  DOI：10.1021/jp2022693

  日期：2011.7.28

  Urea compounds are useful anion sensors due to their hydrogen-bonding capabilities. We investigated the emissive properties of complexes consisting of urea anthracene (nPUA, n = 1, 2) host compounds and acetate anions held as guests through intermolecular hydrogen bonding. The kinetics of a new emission band formed by conformational changes in the excited singlet state were revealed. The new band is thought to arise from a charge-transfer interaction between the anthracene and urea moieties after intermolecular hydrogen-bond reconfiguration in the excited state, with rate constants of 2.4 x 10(9) and 4.0 x 10(7) s(-1) for 1PUA and 2PUA, respectively.
• 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-.