triptycene-1,4-quinone | 1711-46-2

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: triptycene-1,4-quinone
• 英文别名: Pentacyclo[6.6.6.02,7.09,14.015,20]icosa-4,9,11,13,15,17,19-heptaene-3,6-dione
• CAS: 1711-46-2
• 化学式: C₂₀H₁₄O₂
• 分子量: 286.33
• InChiKey: WHGYFGNRTSDCBM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  triptycene-1,4-quinone 在 溴 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 6.5h， 生成 9,10-dihydro-1,4-dihydroxy-9,10[1',2']-benzenoanthracene-2,3-dicarbonitrile
  参考文献：
  名称：

  Synthesis, Photochemistry, and Electrochemistry of a Series of Phthalocyanines with Graded Steric Hindrance

  摘要：

  A group of twelve new and three known silicon phthalocyanines having axial ligands and peripheral groups which provide varying amounts of steric protection to the ring face and ring periphery has been assembled. These are SiPc[OSi(n-C6H13)(3)](2), 1, (known), SiPc[OSi(i-C4H9)(2)(n-C18H37)](2), 2, SiPc(OEt)(8)[OH](2), 5, SiPc(OEt)(8)[OSi(CH3)(3)](2), 6, SiPc(OnBu)(8)[OH](2), 8, (known), SiPc(OnBu)(8)[OSi(n-C6H13)(3)](2), 9, (known), SiPc(OnBu)(8)[OSi(i-C4H9)(2)(n-C18H37)](2), 10, SiPc(dib)(4)(OnBu)(8)[OH](2), 15, SiPc(dib)(4)(OnBu)(8)[F](2), 16, SiPc(dib)(4)(OnBu)(8)[OSi(n-C6H13)(2)](2), 17, SiPc(dib)(4)(OnBu)(8)[OSi(i-C4H9)(2)(n-C18H37)](2), 18, SiPc(dib)(4)(OnBu)(8)[OSi8O12(C5H9)(7)](2), 19, SiPc(dib)(4)(OnBu)(8)[OH](2), 22, SiPc(dib)(4)(OiBu)(8)[OSi(n-C6H13)(3)](2), 23, and SiPc(dib)(4)(OiBu)(8)[OSi8O12(C5H9)(7)](2), 24. Syntheses are given for the twelve members of the group that are new. Photophysical and voltammetric investigations of six representative members of the group, 1, 2, 10, 18, 19, and 24, have been carried out. The results show that compounds 1 and 2 (no butoxy substituents at the I and 4 positions) have significantly larger values of the first oxidation potential (E+1) than those compounds (10, 18, 19, and 24) that do carry these substituents. The values of E-1 (first reduction potential) show very little in the way of structural dependence. Alkoxy substitution at the 1,4 positions affects the HOMO energies, and therefore, the addition of an electron from an electrode to the LUMO of a 1,4 substituted silicon phthalocyanine will not be a sensitive function of the substitution pattern. The removal of an electron from the HOMO in an oxidation step on the other hand would be expected to be energetically less demanding for those compounds wherein the HOMO is higher lying. This orbital energy effect of substitution makes it clear why the E+1 values for compounds 1 and 2 are significantly lower. Substitution of dibenzobarreleno (dib) at the 2,3 positions has only minor effects on the HOMO energy, as shown by the similarities in the position of the Q-band maximum. However, it is very likely that the steric effects of the dibenzobarreleno substituents and the [OSi8O12(C5H9)(7)] axial cages contribute to the observed trends in E+1. Bimolecular rate constants for quenching of the triplet states of the six target compounds by O-2, by beta-carotene, and by chloranil were measured. The first two compounds quench by triplet-triplet (TT) energy transfer, whereas the last is an electron transfer (ET) reactant. All rate parameters were sensitive to the steric crowding of the phthalocyanine pi system, but with different degrees. The least sensitive was the ET reaction with chloranil.Thus, it appears that although steric crowding of the triplet state of the silicon phthalocyanines is very effective at reducing the rate constants of exoergic electron exchange energy transfer (TT) reactions, even for a small molecule such as oxygen, it is much less effective at discriminating against electron transfer (ET) processes. These differences may be accounted for on the concept that the overlap requirement for the double electron exchange of TT energy transfer is more stringent compared to the single electron transfer (ET).

  DOI：

  10.1021/jp027006q
• 作为产物：
  描述：

  蒽 、 对苯醌 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 5.0h， 以88%的产率得到triptycene-1,4-quinone
  参考文献：
  名称：

  含三茂铁的共聚酯的熔融相合成及其性能

  摘要：

  合成了一种新的三萜烯二醇（TD），即三萜烯1，，4-对苯二酚-双（2-羟乙基）醚，并通过以下方法与1,4-环己烷二甲酸二甲酯（1,4-DMCD）制备了一系列共聚酯熔融缩聚。直链脂族间隔基，包括乙二醇（EG），1,4-丁二醇（BD）和1,6-己二醇（HD），与TD一起用作共二醇，以探索直链柔性间隔基对共聚酯性能的影响。基于对苯二酚双（2-羟乙基）醚（HBE），双[4-（2-羟乙氧基）苯基]砜（BHPS），1,1-双[4-（2-羟乙氧基）的非三茂共聚酯系列制备[]苯基]环己烷（BHPC）或1,1-双（2-羟基乙氧基）苯基-3,3,5-三甲基环己烷（BHPT）进行比较。T g ’s）。对于含三萜烯的共聚酯，发现机械性能取决于共聚单体二醇的类型和组成。观察到基于1,4-丁二醇的三茂铁共聚酯的T g和模量显着增加，同时在环境温度（23°C）下保持较高的伸长率。但是，所有研究的基于1,4-丁二醇的共聚

  DOI：

  10.1021/ma2004025

文献信息

• Synthesis and characterization of triptycene-based polyimides with tunable high fractional free volume for gas separation membranes
  作者：Jennifer R. Wiegand、Zachary P. Smith、Qiang Liu、Christopher T. Patterson、Benny D. Freeman、Ruilan Guo

  DOI：10.1039/c4ta02303j

  日期：——

  Triptycene-containing polyimide membranes with tunable fractional free volume promoting fast gas transport and selective separations.

  含有三环芳烃的聚酰亚胺膜，可调节的自由体积分数促进快速气体传输和选择性分离。
• Quinone-Based, Redox-Active Resorcin[4]arene Cavitands
  作者：Igor Pochorovski、Corinne Boudon、Jean-Paul Gisselbrecht、Marc-Olivier Ebert、W. Bernd Schweizer、François Diederich

  DOI：10.1002/anie.201106031

  日期：2012.1.2

  Catch it if you can! Redox‐active resorcin[4]arene cavitands with quinone walls can be reversibly reduced to the hydroquinone form, influencing their host–guest complexation strength. Specifically, a top‐covered triptycenequinone cavitand forms kinetically stable complexes with cycloalkanes; this complexation is weaker in the reduced hydroquinone form.

  如果可以的话赶上它！具有醌壁的氧化还原活性间苯二酚[4]芳烃空洞可被可逆地还原为对苯二酚形式，影响它们的主客体络合强度。特别是，顶部覆盖的三烯醌卡维酮与环烷烃形成动力学稳定的络合物。在还原的对苯二酚形式中，这种络合作用较弱。
• Metal Ion-Catalyzed Diels−Alder and Hydride Transfer Reactions. Catalysis of Metal Ions in the Electron-Transfer Step
  作者：Shunichi Fukuzumi、Kei Ohkubo、Toshihiko Okamoto

  DOI：10.1021/ja026417h

  日期：2002.11.1

  to p-benzoquinones with those in the Diels-Alder reactions of the quinones as well as the hydride-transfer reactions has revealed that the catalysis of metal ions in each case is ascribed to the 1:1 and 1:2 complexes formed between the corresponding semiquinone radical anions and metal ions. The transient absorption and ESR spectra of the semiquinone radical anion-metal ion complexes are detected directly

  在金属存在下，蒽与对苯醌及其衍生物的 Diels-Alder 环加成速率以及从 10-甲基-9,10-二氢吖啶到同一系列对苯醌的氢化物转移反应的速率显着加快乙腈中的离子。金属离子在从单电子还原剂（钴四苯基卟啉和十甲基二茂铁）到对苯醌的电子转移中的催化作用与醌类的 Diels-Alder 反应以及氢化物转移反应中的催化作用的广泛比较表明，在每种情况下，金属离子的催化作用都归因于相应的半醌自由基阴离子与金属离子之间形成的 1:1 和 1:2 络合物。在金属离子存在下对苯醌衍生物的电子转移还原中直接检测到半醌自由基阴离子-金属离子络合物的瞬态吸收和 ESR 光谱。由于 O(2)(.-) 和 M(n+) 之间的络合物形成，每个反应中各种金属离子的催化反应性与 pi(g) 能级的能量分裂值密切相关，其来源于O(2)(.-)-M(n+) 复合物的 ESR 光谱的 g(zz) 值。
• TRIPTYCENE MONOMER AND TRIPTYCENE CONTAINING POLYESTERS AND POLYURETHANES
  申请人：Turner S. Richard

  公开号：US20150191408A1

  公开（公告）日：2015-07-09

  The primary diol triptycene derivative triptycene-1,4-hydroquinone-bis(2-hydroxyethyl) ether (TD) is provided, as are methods of using the same to synthesize polyesters and polyurethanes, and polyesters and polyurethanes synthesized therewith.

  提供了主要二醇三萜衍生物三萜-1,4-对苯二酚-双(2-羟乙基)醚(TD)，以及使用该物质合成聚酯和聚氨酯的方法，以及由此合成的聚酯和聚氨酯。
• Hybrid Molecular Container Based on Glycoluril and Triptycene: Synthesis, Binding Properties, and Triggered Release
  作者：Wenjin Liu、Xiaoyong Lu、Weijian Xue、Soumen K. Samanta、Peter Y. Zavalij、Zihui Meng、Lyle Isaacs

  DOI：10.1002/chem.201802981

  日期：2018.9.20

  We designed and synthesized a “hybrid” molecular container 1, which is structurally related to both cucurbit[n]uril (CB[n]) and pillar[n]arene type receptors. Receptor 1 was fully characterized by 1H NMR, 13C NMR, IR, MS and X‐ray single crystal diffraction. The self‐association behavior, host–guest recognition properties of 1, and the [salt] dependence of Ka were investigated in detail by 1H NMR and

  我们设计并合成了一个“杂交”分子容器1，该容器在结构上与葫芦[ n ] uril（CB [ n ]）和支柱[ n ]芳烃型受体有关。受体1通过1 H NMR，13 C NMR，IR，MS和X射线单晶衍射进行了充分表征。的自缔合的行为，主客体识别属性1，和的[盐]的依赖性ķ一个在通过详细研究1 H NMR和等温滴定量热法（ITC）。光学透射率和TEM测量提供了有力的证据证明受体1与两亲性客体C10在水中共组装，形成超分子双层囊泡（直径25.6±2.7 nm，壁厚≈3.5 nm），可以包裹亲水性抗癌药阿霉素（DOX）和疏水性染料尼罗红（NR）。六甲铵（8 c）或精胺（10）可以触发囊化的DOX或NR的释放，从而导致超分子囊泡的破坏。