2,5-bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]thiophene | 137251-06-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,5-bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]thiophene
• 英文别名: 9-[5-(9-Hydroxyfluoren-9-yl)thieno[3,2-b]thiophen-2-yl]fluoren-9-ol
• CAS: 137251-06-0
• 化学式: C₃₂H₂₀O₂S₂
• 分子量: 500.642
• InChiKey: MKXNJGVGDUOWKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  36
• 可旋转键数：
  2
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  96.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,5-bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]thiophene 在 氢碘酸 、 乙酸酐 、 溶剂黄146 作用下， 反应 1.5h， 以55%的产率得到2,5-Bis-(9H-fluoren-9-yl)-thieno[3,2-b]thiophene
  参考文献：
  名称：

  Thermal and photochemical formation of quinonoid derivatives of condensed polythiophenes and their spectral properties

  摘要：

  Quinonoid derivatives of linearly condensed thiophenes have been prepared from the precusor diols thermally as well as photochemically and their spectral characteristics are demonstrated.

  DOI：

  10.1016/s0040-4039(00)92172-5
• 作为产物：
  描述：

  2,5-二溴噻吩并[3,2-B]噻吩 、 9-芴酮 在 正丁基锂 作用下， 生成 2,5-bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]thiophene
  参考文献：
  名称：

  Clathrate Formations with Isomeric Host Compounds Based on Thieno[3,2-b]thiophene and Thieno[2,3-b]thiophene: Inclusion Modes and Crystal Structures

  摘要：

  Two host compounds 1 and 2, which are composed of isomeric thieno[3,2-b]thiophene and thieno[2,2-b]thiophene, respectively, afforded crystalline host-guest inclusion complexes. Benzene and DMSO were chosen as guest species capable of the least and the most intense host-guest interactions, respectively, and the X-ray crystal structures of their clathrates were investigated. Benzene was enclathrated in each of 1 and 2 with different host-to-guest ratios to give (1)(3)(benzene)(4) and(a)(benzene). In both crystals, there are pairs of benzene molecules arranged in parallel offset. Crystal data: (1)(3)(benzene)(4), triclinic, P $($) over bar$$ 1, a = 13.940(5)Angstrom, b = 15.537(2)Angstrom, c = 13.040(4)Angstrom, alpha = 104.13(2)degrees, beta = 119.91(2)degrees, gamma = 92.24(2)degrees, V = 2330(1)Angstrom(3), Z = 1; (2)(benzene), triclinic, P $($) over bar$$ 1, a = 12.427(4)Angstrom, b = 13.041(4)Angstrom, c = 10.733(2)Angstrom, alpha = 92.97(2)degrees, beta = 104.79(2)degrees, gamma = 117.10(1)degrees, V = 1648.2(7)Angstrom(3), Z = 2. The(2)(benzene) crystals eliminate the guest at significantly high temperature, 128 degrees C, which is discussed in light of the hydrogen-bonded rigid host lattices. The crystals including DMSO, (1)(DMSO)(2), and (2)(DMSO)(2) were isomorphous. Crystal data: (1)(DMSO)(2), triclinic, P $($) over bar$$ 1, a = 12.618(1)Angstrom, b = 13.161(2)Angstrom, c = 11.615(3)Angstrom, alpha = 115.41(2)degrees, beta = 97.04(2)degrees, gamma = 103.41(1)degrees, V = 1639.7(6)Angstrom(3), Z = 2; (2)(DMSO)(2), triclinic, P $($) over bar$$ 1, a = 12.613(1)Angstrom, b = 13.383(3)Angstrom, c = 11.601(2)Angstrom, alpha = 115.49(1)degrees, beta = 97.28(1)degrees, gamma = 104.60(1)degrees, V = 1647.3(5)Angstrom(3), Z = 2. The formation of the isostructural crystals is discussed on the basis of the strong hydrogen bonding between the host and guest molecules, which counteracts the structural and electronic differences between 1 and 2. In line with this interpretation, the conformational preference of the OC-CS bonds due to the electrostatic O ... S attraction was overcome in the DMSO inclusion crystals. In spite of the isostructural crystal packing, their thermal behavior of guest release, as investigated by DSC measurements, is rather different; (1)(DMSO)(2) loses the guest DMSO molecules stepwise at 111 and 138 degrees C, whereas (2)(DMSO)(2) does at 96 and 159 degrees C.

  DOI：

  10.1021/jo00125a020

文献信息

• Solid-State Solvolysis of Thiophene-Substituted Trityl-Type Alcohols:  Nucleophilic Substitution Induced by Gas−Solid Contact
  作者：Motoko Tanaka、Naoki Tanifuji、Shigeru Hatada、Keiji Kobayashi

  DOI：10.1021/jo001291x

  日期：2001.2.1

  suggested by the ESR spectrum. The mechanism involving the collapse of the radical cation to generate a proton, which acts as a catalyst to afford the carbocation, was deduced based on the electrochemical oxidation of the substrate in solution. The propagation of the substitution reaction in the solid state has been shown for the carbocation upon contact with methanol vapor. The crystalline inclusion

  已经研究了通过气固接触的亲核取代反应。当将9-噻吩并噻吩芴-9-ol衍生物与二氯二氰基醌（DDQ）共研磨，然后暴露于甲醇蒸气中时，以15-70％的产率获得相应的9-甲氧基芴。在整个过程中，固态保持不变。ESR光谱表明，通过底物醇与DDQ之间的电荷转移相互作用，在共研磨的固体中生成了自由基阳离子。基于溶液中底物的电化学氧化，推导了涉及自由基阳离子分解产生质子的机理，该质子充当提供碳正离子的催化剂。对于与甲醇蒸气接触的碳正离子，已经显示出固态的取代反应的传播。将以甲醇为客体的9-噻吩并噻吩基芴-9-醇衍生物的结晶包合物暴露于HCl气体中。该气固反应还导致形成保持固态的相应甲氧基化合物。通过这项工作，得出了固态共研磨的新结果。
• Solid-state solvolysis induced via charge-transfer complexation by solid-phase grinding followed by contact with solvent vapor
  作者：Motoko Tanaka、Keiji Kobayashi

  DOI：10.1039/a803496f

  日期：——

  When 9-thienothienylfluoren-9-ol derivatives were ground together with DDQ then exposed to methanol vapor, solvolysis occurred to yield 9-methoxyfluorenes via the generation of a radical cation by solid-state single-electron transfer.

  当9-噻吩噻吩基荧光醇衍生物与DDQ共同研磨后暴露于甲醇蒸气中时，发生了亲核溶解反应，通过固态单电子转移生成自由基阳离子，从而生成9-甲氧基荧光素。
• Tanaka, Motoko; Kobayashi, Keiji, Phosphorus, Sulfur and Silicon and the Related Elements, 1999, vol. 153, p. 371 - 372
  作者：Tanaka, Motoko、Kobayashi, Keiji

  DOI：——

  日期：——
• Fluorescent Molecular Complexes of 9-Hydroxyfluoren-9-yl Substituted Thiophene and Thienothiophenes with 1,2,4,5-Tetracyanobenzene:Crystalline Complexation of Bulky and Conformationally Mobile Molecules
  作者：Naoto Hayashi、Keiji Kobayashi

  DOI：10.1080/10587259608039373

  日期：1996.2

  Bis(9-hydroxyfluoren-9-yl)-substituted thiophene (1), thieno-[3,2-b]thiophene (2), and thieno[2,3-b]thiophene (3) were recrystallized with 1,2,4,5-tetracyanobenzene (TCNB) from CH2Cl2 to afford crystalline complexes (1)(2)(TCNB), (2)(TCNB)(CH2Cl2), and (3)(TCNB)(CH2Cl2), respectively. These crystals are yellow and fluorescent in the solid state. X-ray analyses of (1)(2)(TCNB) and (3)(TCNB)(CH2Cl2) revealed that the fluorenyl moieties and the TCNB ring are arranged in a face-to-face manner. The coloring and fluorescent properties are ascribed to a weak charge-transfer (CT) interaction, which is brought about by lattice controlled packing rather than intrinsic CT interactions. The nature of the fluorescence is discussed on the basis of the crystal structure and the lifetime of the emission.
• Solid-State Photosolvolysis of Clathrate Crystals Including Ethanol as a Guest Component
  作者：Naoto Hayashi、Yasuhiro Mazaki、Keiji Kobayashi

  DOI：10.1080/10587259408027166

  日期：1994.6

  A simple bimolecular photosubstitution at a saturated carbon atom of the host by the guest molecule has been observed in the clathrate crystals which are composed of 9-fluorenyl substituted thienothiophenes as a host component and include ethanol as a guest species. Based on the X-ray analyses, topochemical characteristics of this novel solid-state photosolvolysis are discussed.