(Z)-1,4-bis(4-fluorophenyl)but-2-ene-1,4-dione

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-1,4-bis(4-fluorophenyl)but-2-ene-1,4-dione
• 化学式: C₁₆H₁₀F₂O₂
• 分子量: 272.251
• InChiKey: OXUZAAMYHTYRBZ-KTKRTIGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (Z)-1,4-bis(4-fluorophenyl)but-2-ene-1,4-dione 在 10percent Pd/C 硝酸 、 铁粉 、 氯化铵 、 溶剂黄146 、 环己烯 作用下， 以 1,4-二氧六环 、 N-甲基吡咯烷酮 、 乙醇 、 水 、 甲苯 为溶剂， 反应 1.75h， 生成 3,5-bis(3-formamido-4-fluorophenyl)-4-azatricyclo[5.2.1.0^2,6]deca-2,5-diene
  参考文献：
  名称：

  1,3-Diaryl-4,5,6,7-tetrahydro-2H-isoindole Derivatives:  A New Series of Potent and Selective COX-2 Inhibitors in Which a Sulfonyl Group Is Not a Structural Requisite

  摘要：

  Novel tetrahydro-2H-isoindoles have been prepared and evaluated as inhibitors of the COX-2 isoenzyme. A 1,S-diaryl substitution on the central polycyclic ring system and absence of a sulfonyl moiety are the two structural features of this chemical series. A short and easy synthetic pathway produced several derivatives which were shown to be potent and selective COX-2 vs COX-1 inhibitors (IC50 = 0.6-100 nM for COX-2, 100->1000 nM for COX-1). Structural modifications established that a bicyclic ring appended to the pyrrole nucleus and 4,4'-difluoro substitution on the phenyl rings were optimal for high inhibitory potency. Activity was confirmed in the human whole blood assay and subsequently in the murine air-pouch model in which in vivo PGE2 inhibitory activity was evaluated with respect to gastric tolerance (ED50 for inhibition of exudate PGE2 of 3 mg/kg and gastric PGEB of 20 mg/kg). Gastric tolerance was further assessed after administration to mice of high doses (up to 400 mg/kg) of the inhibitors by measurement of gastric damage. This panel of studies allowed selection of a number of tetrahydro-2H-isoindoles which were compared in the adjuvant-induced arthritis model. Compounds 32 and 37 showed the most potent activity with ED50 values for edema inhibition in the noninjected paw of 0.35 and 0.15 mg/kg/day, respectively, after oral administration. In addition, this interesting antiinflammatory profile was accompanied by a protective effect against arthritis-induced osteopenia, the decrease being 50% with a dose of 0.25 mg/kg/day.

  DOI：

  10.1021/jm990965x
• 作为产物：
  描述：

  (E)-1,4-bis(4-fluorophenyl)but-2-ene-1,4-dione 以 溶剂黄146 为溶剂， 生成 (Z)-1,4-bis(4-fluorophenyl)but-2-ene-1,4-dione
  参考文献：
  名称：

  Influences of fluorination on homoleptic iridium complexes with C∧N=N type ligand to material properties, ligand orientation and OLED performances

  摘要：

  两种具有 C∧N=N 型配体的新铱配合物（即Ir(BFPPya)3{三[3,6-双（4-氟苯基）哒嗪]铱（III）}和 Ir(BDFPPya)3{三[3,6-双（2,4-二氟苯基）哒嗪]铱（III）}），并研究了氟化对材料性质和器件性能的影响。与我们之前报道的无氟类似材料，即 Ir(BPPya)3{三[3,6-双（苯基）哒嗪]铱（III）}相比，在发射光谱和长波长吸收区都观察到了蓝移。配体氟化后，光致发光量子产率（PLQY）（0.44 和 0.84 vs 0.29）、磷光寿命（0.88 和 1.31 vs 0.66 ms）和氧化电位（1.10 和 1.37 vs 0.95 V）明显增加。相反，铱配合物的热稳定性略有下降（Td：435 和 402 vs 440 ℃）。在密度泛函理论（DFT）计算中，通过比较一个优化分子中三种配体的立体形状，观察到了不同配合物之间的取向差异。在 OLED 器件研究中，使用 TPBI [2,2′,2″-（1,3,5-苯三基）三（1-苯基-1H-苯并咪唑）] 电子传递宿主和最氟掺杂剂 Ir(BDFPPya)3 实现了蓝绿色电致发光，峰值发射为 500 nm，最大效率为 20.3 cd/A。一方面，考虑到 0.84 的高 PLQY，这一效率并不令人满意。另一方面，由于器件结构相似，所有掺杂剂的（HOMO-LUMO）都包裹在宿主 TPBI 的（HOMO-LUMO）内，而且所有掺杂剂的三重能都小于宿主 TPBI 的三重能，因此器件效率的排序与 PLQY 的排序是矛盾的。借助 TPBI 的磷光光谱和掺杂剂的吸收光谱，可以合理地解释这一矛盾。

  DOI：

  10.1007/s11426-014-5172-1

文献信息

• Visible-Light-Mediated Oxidative Dimerization of Arylalkynes in the Open Air: Stereoselective Synthesis of (<i>Z</i>)-1,4-Enediones
  作者：Donglei Wei、Fushun Liang

  DOI：10.1021/acs.orglett.6b02926

  日期：2016.11.18

  An organic photoredox catalytic one-pot protocol is developed for the highly stereoselective synthesis of (Z)-1,4-enediones. The reaction starts directly from alkyne precursors, using 4-(4-cyanophenyl)-2,6-diphenylpyrylium tetrafluoroborate (CN-TPT) as an efficient photosensitizer and dioxygen in the air as a green oxidant. A Csp–Csp oxidative coupling/[4 + 2] cyclization (with dioxygen)/fragmentive

  开发了一种有机光氧化还原催化一锅法，用于高度立体选择性地合成（Z）-1,4-二烯酮。该反应直接从炔烃前体开始，使用四氟硼酸4-（4-氰基苯基）-2,6-二苯基吡啶鎓（CN-TPT）作为有效的光敏剂，并在空气中使用双氧作为绿色氧化剂。提出了AC sp –C sp氧化偶合/ [4 + 2]环化（含双氧）/碎片异构化的级联机理。（Z）-1，4-二烯的主要形成归因于来自蓝色LED的有效可见光照明，以及可能的从光敏剂CN-TPT到E-异构体的能量转移。
• Photoredox-Mediated Aerobic Oxidative Cleavage of 1,3-Diketones to Access 1,2-Diketones and (<i>Z</i>)-1,4-Enediones
  作者：Xiaofeng Yu、Nan Huang、Yanping Huo、Xianwei Li、Yan Liu、Keiji Maruoka、Qian Chen

  DOI：10.1021/acs.orglett.3c04247

  日期：2024.1.19

  is disclosed. The newly developed reaction provides practical access to 1,2-diketones and (Z)-1,4-enediones in moderate to good yields with absolute regio- and stereoselectivity. Mechanistic studies of the reaction suggest that tetraketone intermediates might undergo a photocatalytic energy transfer from the excited photocatalyst to form biradical-like (n,π*) states of ketones.

  公开了使用有机染料作为光催化剂在可见光照射下1,3-二酮的有氧氧化裂解。新开发的反应以中等至良好的产率和绝对的区域选择性和立体选择性提供了实际获得 1,2-二酮和 ( Z )-1,4-烯二酮的方法。该反应的机理研究表明，四酮中间体可能会经历激发光催化剂的光催化能量转移，形成酮的双自由基 (n,π*) 态。
• 一种1,2-二酮衍生物与顺-2-烯-1,4-二酮衍生物同时合成的方法
  申请人：广东工业大学

  公开号：CN117209345A

  公开（公告）日：2023-12-12

  本专利申请公开了一种1,2‑二酮衍生物与顺‑2‑烯‑1,4‑二酮衍生物同时合成的方法：通过将二苯甲酰基甲烷及其衍生物在可见光下异构化同时生成1,2‑二酮衍生物与顺‑2‑烯‑1,4‑二酮衍生物。合成方法概述如下：将二苯甲酰基甲烷及其衍生物、赤藓红B钠盐和一个当量的无机碱溶于有机溶剂中，在氧气氛围、在12W蓝光照射下反应24小时，最后经后处理分离纯化得到1,2‑二酮衍生物与顺‑2‑烯‑1,4‑二酮衍生物。本专利申请的合成方法具有操作简便、收率较高、反应经济性高、对环境友好等显著优点。
• 1,3-Diaryl-4,5,6,7-tetrahydro-2<i>H</i>-isoindole Derivatives:  A New Series of Potent and Selective COX-2 Inhibitors in Which a Sulfonyl Group Is Not a Structural Requisite
  作者：Bernard Portevin、Charles Tordjman、Philippe Pastoureau、Jacqueline Bonnet、Guillaume De Nanteuil

  DOI：10.1021/jm990965x

  日期：2000.11.1

  Novel tetrahydro-2H-isoindoles have been prepared and evaluated as inhibitors of the COX-2 isoenzyme. A 1,S-diaryl substitution on the central polycyclic ring system and absence of a sulfonyl moiety are the two structural features of this chemical series. A short and easy synthetic pathway produced several derivatives which were shown to be potent and selective COX-2 vs COX-1 inhibitors (IC50 = 0.6-100 nM for COX-2, 100->1000 nM for COX-1). Structural modifications established that a bicyclic ring appended to the pyrrole nucleus and 4,4'-difluoro substitution on the phenyl rings were optimal for high inhibitory potency. Activity was confirmed in the human whole blood assay and subsequently in the murine air-pouch model in which in vivo PGE2 inhibitory activity was evaluated with respect to gastric tolerance (ED50 for inhibition of exudate PGE2 of 3 mg/kg and gastric PGEB of 20 mg/kg). Gastric tolerance was further assessed after administration to mice of high doses (up to 400 mg/kg) of the inhibitors by measurement of gastric damage. This panel of studies allowed selection of a number of tetrahydro-2H-isoindoles which were compared in the adjuvant-induced arthritis model. Compounds 32 and 37 showed the most potent activity with ED50 values for edema inhibition in the noninjected paw of 0.35 and 0.15 mg/kg/day, respectively, after oral administration. In addition, this interesting antiinflammatory profile was accompanied by a protective effect against arthritis-induced osteopenia, the decrease being 50% with a dose of 0.25 mg/kg/day.
• Influences of fluorination on homoleptic iridium complexes with C∧N=N type ligand to material properties, ligand orientation and OLED performances
  作者：Chen Liu、Le Mao、HaoXin Jia、ZhangJin Liao、HongJiao Wang、BaoXiu Mi、ZhiQiang Gao

  DOI：10.1007/s11426-014-5172-1

  日期：2015.4

  Two new iridium complexes with C∧N=N type ligand (i.e., Ir(BFPPya)3tris[3,6-bis(4-fluorophenyl)pyridazine]iridium(III)} and Ir(BDFPPya)3tris[3,6-bis (2,4-di-fluorophenyl)pyridazine]iridium(III)}) attaching with fluorine atoms, were synthesized and the effects of fluorination on the material properties and device performance were investigated. Compared with our previously reported fluorine-free analogue material, that is Ir(BPPya)3tris[3,6-bis(phenyl)pyridazine]iridium(III)}, blue shifts in the emission spectra as well as in the long wavelength region of the absorptions were observed. The photoluminescence quantum yield (PLQY) (0.44 and 0.84 vs 0.29), phosphoresces lifetime (0.88 and 1.31 vs 0.66 ms), and oxidation potential (1.10 and 1.37 vs 0.95 V) increased obviously after fluorinating the ligand. In contrast, the thermal stability of the iridium complexes decreased slightly (Td: 435 and 402 vs 440 °C). In the density functional theory (DFT) calculations, by comparing the steric shape of the three ligands within one optimized molecule, orientational differences among the complexes were observed. In OLED device studies, bluish green electroluminescence with peak emission of 500 nm, using the electron-transporting host of TPBI [2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl- 1H-benzimidazole)] and the most fluorinated dopant of Ir(BDFPPya)3, was achieved with maximum efficiency of 20.3 cd/A. On one hand this efficiency is not satisfactory considering a high PLQY of 0.84. On the other hand with the similar device structure, that the (HOMO-LUMO)s of all the dopants are wrapped within that of the host TPBI, and all the triplet energies of the dopants are smaller than that of the host TPBI, it is abnormal that the ordering of device efficiencies is contradictory to that of PLQY. Assisting with the phosphorescent spectrum of TPBI and the absorption spectra of the dopant, the contradiction was interpreted reasonably.

  两种具有 C∧N=N 型配体的新铱配合物（即Ir(BFPPya)3三[3,6-双（4-氟苯基）哒嗪]铱（III）}和 Ir(BDFPPya)3三[3,6-双（2,4-二氟苯基）哒嗪]铱（III）}），并研究了氟化对材料性质和器件性能的影响。与我们之前报道的无氟类似材料，即 Ir(BPPya)3三[3,6-双（苯基）哒嗪]铱（III）}相比，在发射光谱和长波长吸收区都观察到了蓝移。配体氟化后，光致发光量子产率（PLQY）（0.44 和 0.84 vs 0.29）、磷光寿命（0.88 和 1.31 vs 0.66 ms）和氧化电位（1.10 和 1.37 vs 0.95 V）明显增加。相反，铱配合物的热稳定性略有下降（Td：435 和 402 vs 440 ℃）。在密度泛函理论（DFT）计算中，通过比较一个优化分子中三种配体的立体形状，观察到了不同配合物之间的取向差异。在 OLED 器件研究中，使用 TPBI [2,2′,2″-（1,3,5-苯三基）三（1-苯基-1H-苯并咪唑）] 电子传递宿主和最氟掺杂剂 Ir(BDFPPya)3 实现了蓝绿色电致发光，峰值发射为 500 nm，最大效率为 20.3 cd/A。一方面，考虑到 0.84 的高 PLQY，这一效率并不令人满意。另一方面，由于器件结构相似，所有掺杂剂的（HOMO-LUMO）都包裹在宿主 TPBI 的（HOMO-LUMO）内，而且所有掺杂剂的三重能都小于宿主 TPBI 的三重能，因此器件效率的排序与 PLQY 的排序是矛盾的。借助 TPBI 的磷光光谱和掺杂剂的吸收光谱，可以合理地解释这一矛盾。