1,2,4,5-tetrafluoro-3,6-bis(diethylphosphonylmethyl)benzene | 288627-04-3

• 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: 1,2,4,5-tetrafluoro-3,6-bis(diethylphosphonylmethyl)benzene
• 英文别名: tetraethyl ((perfluoro-1,4-phenylene)bis(methylene))bis(phosphonate)；1,4-bis(diethoxyphosphorylmethyl)-2,3,5,6-tetrafluorobenzene
• CAS: 288627-04-3
• 化学式: C₁₆H₂₄F₄O₆P₂
• 分子量: 450.304
• InChiKey: OHRPCVKNRJZILW-UHFFFAOYSA-N

物化性质

• 熔点：
  73-75 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  470.0±45.0 °C(Predicted)
• 密度：
  1.306±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  28
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,2,4,5-tetrafluoro-3,6-bis(diethylphosphonylmethyl)benzene 在 potassium tert-butylate 、 1-羟基苯并三唑 、 一水合肼 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 126.16h， 生成 N¹-(3-((4-(4-(4-(dibutylamino)styryl)-2,3,5,6-tetrafluorostyryl)phenyl)(methyl)amino)propyl)-N³,N⁵-bis(3-(4-methyl-2-oxo-2H-chromen-7-yloxy)propyl)benzene-1,3,5-tricarboxamide
  参考文献：
  名称：

  Intimately bound coumarin and bis(alkylaminostyryl)benzene fragments: synthesis and energy transfer

  摘要：

  A novel trichromophoric assembly was synthesized, where two molecules of 7-alkoxy-4-methylcoumarin, acting as energy donors, were linked at a fixed distance and controlled geometry to an energy-acceptor bis(alkylaminostyryl) unit. Resonance energy transfer between the two different species was demonstrated by a careful spectroscopic analysis. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.01.075
• 作为产物：
  描述：

  1,2,4,5-四氟苯 在 正丁基锂 、 dimethyl sulfide borane 、 三溴化磷 、 对甲苯磺酸 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 5.75h， 生成 1,2,4,5-tetrafluoro-3,6-bis(diethylphosphonylmethyl)benzene
  参考文献：
  名称：

  Fluorinated molecules relevant to conducting polymer research

  摘要：

  The synthesis of versatile fluorine compounds for conducting polymer research on fluorinated materials is presented. 1,2,4,5-Tetrafluorobenzene was converted to 1,2,4,5-tetrafluorobenzaldehyde (1) and protected as an acetal. This gave the acetals 1,2,4,5-tetrafluoro-3(1,3-dioxol-2-yl)benzene (2a) and 1,2,4,5-tetrafluoro-3-(5,5-dimethyl-1,3-dioxan-2-yl)benzene (2b). Compounds 2a and 2b were converted into the semiprotected 2,3,5,6-tetrafluoroterephthaldehydes: 1,2,4,5-tetrafluoro-3-(1,3-dioxol-2-yl)-6-formylbenzene (3a) and 1,2,4,5-tetrafluoro-3-(5,5-dimethyl-1,3-dioxan-2-yl)-6-formylbenzene (3b). While 3a was easily deprotected to give 2,3,5,6-tetrafluoroterephthaidehyde (4) compound 3b proved very resilient to hydrolysis and gave a 1: 1 mixture of 4 and 1,2,4,5-tetrafluoro-3,6-bis(5,5-dimethyl- 1,3-dioxan-2yl)benzene (5). Compound 4 was reduced to 1,2,4,5-tetrafluoro-3,6-dihydroxymethylbenzene (6) and converted into 1,2,4,5-tetrafluoro-3,6-dibromomethylbenzene (7). Compound 7 was finally converted into 1,2,4,5-tetrafluoro-3,6-bis(diethylphosponylmethyl)benzene (8). Compounds 4 and 8 are versatile fluorinated molecules that can be used to replace their hydrogen counterparts in many molecules and materials. To illustrate this compounds 4 and 8 were oligomerised to give partially fluorinated polyphenylenevinylene (9). (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(02)00289-0

文献信息

• Two-Photon Photosensitized Production of Singlet Oxygen:  Sensitizers with Phenylene−Ethynylene-Based Chromophores
  作者：Sean P. McIlroy、Emiliano Cló、Lars Nikolajsen、Peter K. Frederiksen、Christian B. Nielsen、Kurt V. Mikkelsen、Kurt V. Gothelf、Peter R. Ogilby

  DOI：10.1021/jo0482099

  日期：2005.2.1

  Singlet molecular oxygen (a1Δg) has been produced and optically monitored in time-resolved experiments upon nonlinear two-photon excitation of photosensitizers that contain triple bonds as an integral part of the chromophore. Both experiments and ab initio computations indicate that the photophysical properties of alkyne-containing sensitizers are similar to those in the alkene-containing analogues

  单线态分子氧（一个1个Δ克）已经产生并在时间分辨实验在含有三键作为发色团的组成部分的光敏剂的非线性双光子激发光学监测。实验和从头算都表明含炔的敏化剂的光物理性质类似于含烯烃的类似物的光物理性质。然而，最重要的是，与含有双键的类似物相比，含有炔烃部分的敏化剂对单线态氧介导的光氧化反应更稳定。这种增加的稳定性可能是有利的，尤其是对于其中在相对较长的时间段内收集数据的双光子单线态氧成像实验而言。
• Hydrophilic Conjugated Polymers Prepared by Aqueous Horner–Wadsworth–Emmons Coupling
  作者：Zachariah A. Page、Yao Liu、Egle Puodziukynaite、Thomas P. Russell、Todd Emrick

  DOI：10.1021/acs.macromol.5b02501

  日期：2016.4.12

  The synthesis of hydrophilic conjugated polymers typically relies on organometallic coupling methodologies. Here we present an approach to prepare polar poly(arylene–vinylene)s (PAVs) in water using the Horner–Wadsworth–Emmons (HWE) reaction. The additional preparation of discrete arylene vinylene (AVs) afforded insight into HWE kinetics and regioselectivity. Nine novel PAVs and AVs were synthesized

  亲水性共轭聚合物的合成通常依赖于有机金属偶联方法。在这里，我们介绍一种利用霍纳-沃兹沃思-埃蒙斯（HWE）反应在水中制备极性聚（亚芳基-亚乙烯基）（PAV）的方法。离散亚芳基亚乙烯基（AVs）的额外制备提供了对HWE动力学和区域选择性的了解。合成了九种新颖的PAV和AV，以紫外可见吸收和紫外光电子能谱为特征，并研究了它们在传感和光伏应用中的效用。
• Molecular Tuning of Phenylene-Vinylene Derivatives for Two-Photon Photosensitized Singlet Oxygen Production
  作者：Christian B. Nielsen、Jacob Arnbjerg、Mette Johnsen、Mikkel Jo̷rgensen、Peter R. Ogilby

  DOI：10.1021/jo9020216

  日期：2009.12.4

  the sensitizer play an important role in the photosensitized production of singlet oxygen, O2(a1Δg). In this work, we systematically examine the effect of molecular changes in the sensitizer on the efficiency of singlet oxygen production using, as the sensitizer, oligophenylene-vinylene derivatives designed to optimally absorb light in a nonlinear two-photon process. We demonstrate that one cannot always

  取代基的从属特征和敏化剂的性质在光敏生产单线态氧的方面发挥重要作用，O- 2（A 1 Δ克）。在这项工作中，我们系统地研究了敏化剂中分子变化对单线态氧生产效率的影响，使用了设计用于在非线性双光子过程中最佳吸收光的低聚亚苯基-亚乙烯基衍生物作为敏化剂。我们证明，在尝试构建有效的两光子单线态氧敏化剂时，不能总是依靠经验法则指导。相反，由于行为可能会偏离规范，因此通常需要对系统的光物理特性进行全面研究。例如，公认的是，将酮部分引入敏化剂生色团通常导致更有效地产生单线态氧。但是，我们在这里表明，将羰基引入给定的亚苯基-亚乙烯基可以 对产生的单线态氧的收率有不利影响。使用这些分子，我们表明在使用定性对称派生的参数预测一光子吸收光谱和两光子吸收光谱之间的关系时，也必须格外小心。
• Quadrupolar fluorophores with tetrafluorobenzene central electron acceptor
  作者：Jiří Kulhánek、Milan Klikar、Oldřich Pytela、Numan Almonasy、Jiří Tydlitát、Filip Bureš

  DOI：10.1016/j.jfluchem.2021.109735

  日期：2021.3

  polarizability and electronic transparency of the utilized π-linker. The absorption maxima of target chromophores were found within the range of 346 – 412 nm and the emission maxima of emissive derivatives were found within the range of 411 – 499 nm. Novel TFBs were compared with TFBs previously described in the literature. The experimental data are further corroborated by theoretical calculations.

  合成并描述了基于1,2,4,5-四氟苯（TFB）中心电子受体单元和甲氧基噻吩外围供体的七个新型四极发色团。通过热，电化学和光学测量阐明了基本的结构-性质关系。这些表明性质主要受所用的π-连接剂影响。π-接头的变化导致HOMO-LUMO间隙的调节。LUMO清楚地反映了所使用的π-连接剂的平面性，极化性和电子透明度。发现目标发色团的吸收最大值在346 – 412 nm范围内，而发射衍生物的发射最大值在411 – 499 nm范围内。将新型TFB与文献中先前描述的TFB进行了比较。
• A quadrupolar two-photon fluorescent probe for in vivo imaging of amyloid-β plaques
  作者：Cheol Ho Heo、Avik Ranjan Sarkar、Sung Hoon Baik、Tae Sung Jung、Jeong Jin Kim、Hyuk Kang、Inhee Mook-Jung、Hwan Myung Kim

  DOI：10.1039/c6sc00355a

  日期：——

  A quadrupolar two-photon fluorescent probe for in vivo imaging of amyloid-[small beta] plaques is reported.

  报道了一种用于淀粉样蛋白-[小β]斑块体内成像的四极双光子荧光探针。