2,2-Dimethyl-1,3-bis(4'-bromophenyl)-1,3-propanedione | 155886-75-2

• 物质功能分类: 有机原料 - 酮类化合物
• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 2,2-Dimethyl-1,3-bis(4'-bromophenyl)-1,3-propanedione
• 英文别名: 1,3-bis(4-bromophenyl)-2,2-dimethylpropane-1,3-dione
• CAS: 155886-75-2
• 化学式: C₁₇H₁₄Br₂O₂
• 分子量: 410.105
• InChiKey: SPBRWUGTVRNKJA-UHFFFAOYSA-N

物化性质

• 沸点：
  493.4±40.0 °C(Predicted)
• 密度：
  1.563±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-1,3-bis(4'-bromophenyl)-1,3-propanedione 在 一水合肼 作用下， 以 氯仿 为溶剂， 反应 19.0h， 以97%的产率得到3,5-bis(4-bromophenyl)-4,4-dimethyl-4H-pyrazole
  参考文献：
  名称：

  嵌入弯曲对亚苯基单元的1,3-双自由基：单重态对三重态和平面内芳香性

  摘要：

  从基础化学以及材料科学的角度来看，弯曲的π共轭分子和开壳结构引起了人们的极大关注。在这项研究中，研究了嵌入弯曲的环对亚苯基（CPP s）结构DR-（n +3）CPP s（n = 0-5）中的1,3-二基（DR s）的化学性质，以了解自旋-自旋相互作用，单重态与三重态的曲率和系统大小，以及它们的独特特征，例如平面内的芳香性。预测较大的1,3-双基自由基为三重态基态，例如含七和八对亚苯基单元的双基自由基DR - 7CPP（n = 4）和DR - 8CPP（n = 5），通过量子化学计算。发现较小的双基自由基DR-（n +3）CPP s（n = 0-3）具有单重态基态。因此，基态自旋多重性由对亚苯基环的大小控制。DR - 6CPP在其含偶氮的前驱体（AZ - 6CPP）的光化学脱氮中的实验生成证实了其对基态自旋多重性的尺寸效应。）。有趣的是，在较小尺寸的单重态（例如S- DR - 4CPP（n =

  DOI：

  10.1021/jacs.1c01329
• 作为产物：
  描述：

  1,3-双(4-溴苯基)丙烷-1,3-二酮 、 碘甲烷 在 potassium carbonate 作用下， 以 氯仿 、 二甲基亚砜 为溶剂， 反应 12.5h， 以47%的产率得到2,2-Dimethyl-1,3-bis(4'-bromophenyl)-1,3-propanedione
  参考文献：
  名称：

  嵌入弯曲对亚苯基单元的1,3-双自由基：单重态对三重态和平面内芳香性

  摘要：

  从基础化学以及材料科学的角度来看，弯曲的π共轭分子和开壳结构引起了人们的极大关注。在这项研究中，研究了嵌入弯曲的环对亚苯基（CPP s）结构DR-（n +3）CPP s（n = 0-5）中的1,3-二基（DR s）的化学性质，以了解自旋-自旋相互作用，单重态与三重态的曲率和系统大小，以及它们的独特特征，例如平面内的芳香性。预测较大的1,3-双基自由基为三重态基态，例如含七和八对亚苯基单元的双基自由基DR - 7CPP（n = 4）和DR - 8CPP（n = 5），通过量子化学计算。发现较小的双基自由基DR-（n +3）CPP s（n = 0-3）具有单重态基态。因此，基态自旋多重性由对亚苯基环的大小控制。DR - 6CPP在其含偶氮的前驱体（AZ - 6CPP）的光化学脱氮中的实验生成证实了其对基态自旋多重性的尺寸效应。）。有趣的是，在较小尺寸的单重态（例如S- DR - 4CPP（n =

  DOI：

  10.1021/jacs.1c01329

文献信息

• Electronic Substituent Effects on the Acid-Catalyzed [4+ + 2] Cycloaddition of Isopyrazoles with Cyclopentadiene and the Photochemical and Thermal Denitrogenation of the Resulting 1,4-Diaryl-7,7-dimethyl-2,3-diazabicyclo[2.2.1]hept-2-ene Azoalkanes to Bicyclo[2.1.0]pentanes
  作者：Waldemar Adam、Heinrich M. Harrer、Werner M. Nau、Karl Peters

  DOI：10.1021/jo00093a010

  日期：1994.7

  Eight symmetrically disubstituted 3,5-diaryl-4,4-dimethylisopyrazoles 6 with para and meta substituents (OMe, Me, H, F, Cl, Br, CN, NO2) and two unsymmetrically para-substituted derivatives (OMe and NO2; Me and CO(2)Me) were synthesized from the corresponding 1,3-diaryl-2,2-dimethyl-1,3-propanediones 5, which in turn were readily available by 2,2-dimethylation of the diones 4. The acid-catalyzed cycloaddition of cyclopentadiene to the isopyrazoles 6, a Diels-Alder reaction with inverse electron demand, afforded the 1,4-diaryl-substituted gem-dimethyl azoalkanes 7 of the diazabicyco[2.2.1]hept-2-ene (DBH) type. The cycloadduct yields were strongly dependent on the nature of the aryl substituents and highest for the electron-withdrawing substituents. In acidic solution, the azoalkanes showed cycloreversion to generate an equilibrium between isopyrazole 6, cyclopentadiene, and azoalkane 7. For the p-methoxy derivative, cycloreversion was essentially quantitative, whereas only 20% cycloreversion occurred for the para nitro compound. A positive Hammett rho value (rho = 3.24 for 2 equiv of CF3COOH) was determined for the equilibrium constants of the acid-catalyzed [4(+) + 2] cycloaddition. The unsymmetrically substituted isopyrazoles gave two regioisomeric cycloadducts with a slight excess of one isomer. The direct and triplet-sensitized photochemical and thermal denitrogenation of the azoalkanes 7 gave in quantitative yields the 1,4-diaryl-substituted bicyclo[2.1.0]pentanes (BCP) 8 with retention of configuration. The azoalkanes 7 and the housanes 8 are more persistent than the related 1,4-diaryl-substituted DBH and BCP derivatives. The stabilizing effect is rationalized in terms of less favorable benzylic conjugation in the transition states for C-N (azoalkanes) and C-C (housanes) bond cleavage due to steric interactions between the geminal methyl groups at the methane bridge and the diaryl substituents at the bridgehead sites.
• De Novo Design of Excited-State Intramolecular Proton Transfer Emitters via a Thermally Activated Delayed Fluorescence Channel
  作者：Kailong Wu、Tao Zhang、Zian Wang、Lian Wang、Lisi Zhan、Shaolong Gong、Cheng Zhong、Zheng-Hong Lu、Song Zhang、Chuluo Yang

  DOI：10.1021/jacs.8b04795

  日期：2018.7.18

  Developing excited-state intramolecular proton transfer (ESIPT) emitters with high photoluminescence quantum yields (Phi(PL)s) and long fluorescence lifetimes in solid state remains a formidable challenge. In this study, we integrated the molecular design tactics of thermally activated delayed fluorescence (TADF) into ESIPT molecules with the goals of improving their Phi(PL)s and increasing their fluorescence lifetimes. Two proof-of-concept molecules, PXZPDO and DMACP-DO, were developed by adopting symmetric D-pi-A-pi-D molecular architectures (where D and A represent donors and acceptors, respectively) featuring electron donating phenoxazine or a 9,9-dimethyl-9,10-dihydroacridine moiety, an ESIPT core beta-diketone, and phenylene pi-bridges. Both molecules exhibited sole enol-type forms stabilized by intramolecular hydrogen bonds and exhibited a unique and dynamic ESIPT character that was verified by transient absorption analyses. Endowed with distinct TADF features, PXZPDO and DMACPDO showed high Phi(PL)s of 68% and 86% in the film state, coupled with notable delayed fluorescence lifetimes of 1.33 and 1.94 mu s, respectively. Employing these ESIPT emitters successfully achieved maximum external quantum efficiencies (n(ext)s) of 18.8% and 23.9% for yellow and green organic light-emitting diodes (OLEDs), respectively, which represent the state-of-the-art device performances for ESIPT emitters. This study not only opens a new avenue for designing efficient ESIPT emitters with high Phi(PL)s and long fluorescence lifetimes in solid state but also unlocks the huge potential of ESIPT emitters in realizing high-efficiency OLEDs.
• 1,3-Diradicals Embedded in Curved Paraphenylene Units: Singlet versus Triplet State and In-Plane Aromaticity
  作者：Yuki Miyazawa、Zhe Wang、Misaki Matsumoto、Sayaka Hatano、Ivana Antol、Eiichi Kayahara、Shigeru Yamago、Manabu Abe

  DOI：10.1021/jacs.1c01329

  日期：2021.5.19

  interactions and singlet versus triplet state, as well as their unique characteristics such as in-plane aromaticity. A triplet ground state was predicted for the larger 1,3-diradicals, such as the seven- and eight-paraphenylene-unit-containing diradicals DR-7CPP (n = 4) and DR-8CPP (n = 5), by quantum chemical calculations. The smaller-sized diradicals DR-(n+3)CPPs (n = 0–3) were found to possess singlet ground

  从基础化学以及材料科学的角度来看，弯曲的π共轭分子和开壳结构引起了人们的极大关注。在这项研究中，研究了嵌入弯曲的环对亚苯基（CPP s）结构DR-（n +3）CPP s（n = 0-5）中的1,3-二基（DR s）的化学性质，以了解自旋-自旋相互作用，单重态与三重态的曲率和系统大小，以及它们的独特特征，例如平面内的芳香性。预测较大的1,3-双基自由基为三重态基态，例如含七和八对亚苯基单元的双基自由基DR - 7CPP（n = 4）和DR - 8CPP（n = 5），通过量子化学计算。发现较小的双基自由基DR-（n +3）CPP s（n = 0-3）具有单重态基态。因此，基态自旋多重性由对亚苯基环的大小控制。DR - 6CPP在其含偶氮的前驱体（AZ - 6CPP）的光化学脱氮中的实验生成证实了其对基态自旋多重性的尺寸效应。）。有趣的是，在较小尺寸的单重态（例如S- DR - 4CPP（n =