2-(4-tert-butylphenyl)-5-(4-ethynylphenyl)-1,3,4-oxadiazole | 445220-81-5

• 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: 2-(4-tert-butylphenyl)-5-(4-ethynylphenyl)-1,3,4-oxadiazole
• 英文别名: 2-(4-tert-Butylphenyl)-5-(4-ethynylphenyl)-1,3,4-oxadiazole
• CAS: 445220-81-5
• 化学式: C₂₀H₁₈N₂O
• 分子量: 302.376
• InChiKey: IHLQOINDLWHODT-UHFFFAOYSA-N

物化性质

• 熔点：
  146.9-148.0 °C(Solv: ethanol (64-17-5); water (7732-18-5))
• 沸点：
  432.6±55.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  38.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-tert-butylphenyl)-5-(4-ethynylphenyl)-1,3,4-oxadiazole 在 amberlyst-15 resin 、 水 、 zinc(II) iodide 作用下， 以 丙酮 为溶剂， 反应 41.0h， 生成 {3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl}propynal
  参考文献：
  名称：

  带有末端乙炔基或丁二炔基取代基的2,5-二苯基-1,3,4-恶二唑的官能化反应：产品的X射线晶体结构。

  摘要：

  2-（4-叔丁基苯基）-5-（4-乙炔基苯基）-1,3,4-恶二唑1和丁二炔类似物2在碘化锌存在下与原甲酸三乙酯反应生成缩醛衍生物3和4将其用Amberlyst-15在丙酮-水中水解，以高收率得到炔基醛衍生物5和6。4,5-双（甲氧基羰基）-2-三丁基phosph-1,3-二硫代四氟硼酸盐7与5（nBuLi，THF）的反应得到Wittig产物2-（3- [4- [5-（4-tert） -丁基苯基）-1,3,4-恶二唑-2-基]苯基]丙-2-炔基）-1,3-二硫醇-4,5-二甲基二羧酸酯11（33％收率），而其他尝试了Wittig和Horner- Wadsworth-Emmons反应导致醛基意外地从化合物5和6丢失，分别得到1和2。报告了化合物3、4、5和11的X射线晶体结构：所有四个分子的pi系统主要采用平面构象。5和11结构中键长的比较表明，后者的pi共轭扩展。

  DOI：

  10.1039/b315694j
• 作为产物：
  描述：

  2-(4-溴苯基)-5-(4-叔丁基苯基)-1,3,4-恶二唑 在 bis-triphenylphosphine-palladium(II) chloride 、 sodium hydroxide 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.17h， 生成 2-(4-tert-butylphenyl)-5-(4-ethynylphenyl)-1,3,4-oxadiazole
  参考文献：
  名称：

  包含 π-扩展乙炔基-和丁二炔基-2,5-二苯基-1,3,4-恶二唑衍生物的分子线：合成、氧化还原、结构和光电特性

  摘要：

  具有末端乙炔基-(4a,b) 和丁二炔基-(8a,b) 取代基的 2,5-二苯基-1,3,4-恶二唑 (OXD) 衍生物已以高产率合成。2-Methyl-3,5-hexadiyn-2-ol 以前没有被用于合成末端丁二炔。8a 和 8b 的晶体在环境条件下对长期储存非常稳定。8a 的 X 射线晶体结构显示丁二炔部分被芳香部分空间隔离，这解释了高稳定性。两个衍生的pi-共轭分子，Donor-(C[triple bond]C)(n)-OXD (n = 1, 2) 和OXD-(C[triple bond]C)(n)-Donor-(C) [三键]C)(n)-OXD (n = 1) [供体 = 四硫富瓦烯 (TTF)、联噻吩、9-(4,5-二甲基-1,3-二硫醇-2-亚基)芴和三苯胺] , 已使用 Sonogashira 反应合成，并通过 X 射线晶体学、循环伏安法和光学吸收/发射光谱进行表征。OXD

  DOI：

  10.1021/ja0577600

文献信息

• Ethynyl π-extended 2,5-diphenyl-1,3,4-oxadiazoles and 2-phenyl 5-(2-thienyl)-1,3,4-oxadiazoles: synthesis, X-ray crystal structures and optical properties
  作者：Gregory Hughes、David Kreher、Changsheng Wang、Andrei S. Batsanov、Martin R. Bryce

  DOI：10.1039/b407698m

  日期：——

  2-(4-tert-Butylphenyl)-5-(4-ethynylphenyl)-1,3,4-oxadiazole 1 reacts with a series of heteroaryl iodides under standard Sonogashira cross-coupling conditions (Pd[PPh3]2Cl2, CuI, triethylamine, THF) to yield products 2a–g in 40–79% yields (heteroaryl = 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazyl, 5-bromo-2-pyrimidyl, 2-thienyl and 3-thienyl, respectively). Compound 2f was lithiated followed by electrophilic iodination (BuLi, perfluorohexyl iodide) to give 3, which by a two-step sequence gave the terminal ethynylthienyl derivative 5. Conversion of 5 into the terminal ethynylaldehyde derivative 7, via acetal derivative 6, proceeded in high yield. Starting from 2-iodo-5-methoxycarbonylthiophene, a five-step sequence afforded 2-(4-tert-butylphenyl)-5-(4-ethynylthienyl)-1,3,4-oxadiazole 13 (13% overall yield). Reactions of 13 gave terminal pyridyl, pyrazyl, pyrimidyl and thienyl derivatives, analogous to those obtained from 1. Two-fold reaction of 13 with 2,5-diiodothiophene gave the bis(ethynylthienyl)thiophene derivative 15 (30% yield). Solution UV-Vis absorption and photoluminescence spectra establish that replacement of the phenyl ring in the 2,5-diphenyl-1,3,4-oxadiazole series 2a–g by a thienyl ring [i.e. the 2-phenyl-5-(2-thienyl)-1,3,4-oxadiazole series 14a–g] leads to a red shift in the lowest energy band in both the absorption spectra and emission spectra. The X-ray crystal structures of compounds 2d, 2g, 5 and 14d·CHCl3 reveal that the molecular structures are approximately planar although there are substantial differences in the conformations.

  2-(4-叔丁基苯基)-5-(4-乙炔基苯基)-1,3,4-噁二唑1在标准Sonogashira交叉偶联条件下（Pd[PPh3]2Cl2，CuI，三乙胺，THF）与一系列杂环碘化物反应，生成产物2a–g，产率为40–79%（杂环分别为2-吡啶基、3-吡啶基、4-吡啶基、2-吡唑基、5-溴-2-嘧啶基、2-噻吩基和3-噻吩基）。化合物2f经锂化后再进行亲电碘化（BuLi，全氟己基碘）得到3，通过两步序列得到末端乙炔基噻吩衍生物5。将5转化为末端乙炔基醛衍生物7，经过缩醛衍生物6，过程产率高。从2-碘-5-甲氧羰基噻吩出发，经过五步合成得到2-(4-叔丁基苯基)-5-(4-乙炔基噻吩基)-1,3,4-噁二唑13（总产率13%）。13的反应得到了类似于1的末端吡啶基、吡唑基、嘧啶基和噻吩基衍生物。13与2,5-二碘噻吩的双重反应得到双（乙炔基噻吩基）噻吩衍生物15（产率30%）。溶液UV-Vis吸收光谱和光致发光光谱表明，将2,5-二苯基-1,3,4-噁二唑系列2a–g中的苯环替换为噻吩环（即2-苯基-5-(2-噻吩基)-1,3,4-噁二唑系列14a–g）导致吸收光谱和发射光谱中的最低能量带发生红移。化合物2d、2g、5和14d·CHCl3的X射线晶体结构揭示，尽管构象存在较大差异，分子结构大体上是平面型的。
• Oligo(<i>p</i>-phenyleneethynylene) (OPE) Molecular Wires: Synthesis and Length Dependence of Photoinduced Charge Transfer in OPEs with Triarylamine and Diaryloxadiazole End Groups
  作者：Katharine E. Linton、Mark A. Fox、Lars-Olof Pålsson、Martin R. Bryce

  DOI：10.1002/chem.201406080

  日期：2015.3.2

  Steady‐state emission studies on the dyads 1–5 reveal a complicated behavior of the emission that is strongly medium dependent. In low polarity solvents the emission is characterized by a sharp high‐energy peak attributed to fluorescence from a locally excited (LE) state. In more polar environments the LE state is effectively quenched by transfer into an intramolecular charge‐transfer (ICT) state. The

  系统的合成和光物理，电化学和计算研究上的扩展系列triphenylamine- [CC-1,4-C的6 ħ 2（OR）2 ] Ñ -CC二苯基-1,3,4-恶二唑成对层分子（OR基团处于2,5-位置对位亚苯基环，R = C 6 H ^ 13 ; ñ = 0-5，化合物1，2，3，4和5分别）被报告。具有相同端基的相关分子，三苯胺-CC-1,4- C6 H 2（OR）2-CC-三苯胺（R = C 6 H 13 ; 6）和联苯-1,3,4-恶二唑-[CC- C6 H 2（OR）2 ] 2 -CC-二苯基-1还研究了3,4-恶二唑（R = C 6 H 13 ; 7）。这些D–B–A 1 – 5，D–B–D 6和A–B–A 7（D =电子供体，B =桥，A =电子受体）系统是使用钯催化的交叉偶联反应合成的新的对-亚苯基乙炔基砌块。在二元体系稳态排放研究1 - 5揭示了与介质密切相关的复
• Electrochromic tetrathiafulvalene derivatives functionalised with 2,5-diaryl-1,3,4-oxadiazole chromophoresElectronic Supplementary Information (ESI) available: spectroelectrochemistry of 3 and 4; 1H-NMR spectra and cyclic voltammograms for 3, 4 and 5; crystallographic information for 5. See http://www.rsc.org/suppdata/cc/b3/b316243p/
  作者：Changsheng Wang、Andrei S. Batsanov、Martin R. Bryce

  DOI：10.1039/b316243p

  日期：——

  Electrochromism has been demonstrated by three novel electrochemically-reversible compounds 3, 4 and 5, which were synthesised by Pd catalysed cross-coupling of iodotrimethylTTF (6) and 2,6(7)-diiodoTTF (7) with the 2,5-diaryl-1,3,4-oxadiazole derivatives 1 and 2 containing terminal ethyne and butadiyne groups.

  碘三甲基三联苯（6）和 2,6(7)- 二碘三联苯（7）与含有末端乙炔和丁二烯基团的 2,5- 二芳基-1,3,4-恶二唑衍生物 1 和 2 在钯催化下发生交叉偶联，合成了三种新型电化学可逆化合物 3、4 和 5。
• Two-photon absorption chromophores with a tunable [2,2′]bithiophene core
  作者：Chia-Feng Chou、Tai-Hsiang Huang、Jiann T. Lin、Cheng-chih Hsieh、Chin-Hung Lai、Pi-Tai Chou、Chiitang Tsai

  DOI：10.1016/j.tet.2006.06.085

  日期：2006.9

  Sonogashira coupling between 3,5,3',5'-tetrabromo-[2,2']bithiophene and various terminal alkynes provides two-photon absorption (TPA) chromophores 1-6, which possess electron donor (D) and/or acceptor (A) alkynyl substituents at 3(3') and 5(5') sites of the bithiophene core. The up-converted fluorescence emission excited at 800 nn (Ti:sapphire femtosecond laser, similar to 100 fs pulses) was used to determine the two-photon absorption cross-sections (Q) of these compounds. The corresponding TPA cross-section (a) values ranging from 132 to 1120 GM (10(-50) cm(4)s photon(-1)) can be fine-tuned by the substitutents. The quadrupolar-type (A-pi-D-pi-A) chromophore 5 exhibits the largest Q value (1120 GM) in CH2Cl2 upon 800 nm excitation. (c) 2006 Elsevier Ltd. All rights reserved.
• Photochromism of dihydroindolizines. Part XVI: first attempts toward molecular wires comprising photochromic dihydro 5-azaindolizines and π-extended ethynyl and butadiynyl oxadiazole derivatives
  作者：Saleh Abdel-Mgeed Ahmed

  DOI：10.1016/j.tetlet.2009.11.117

  日期：2010.1

  Eight new photochromic dihydro, 5-azaindolizines (DHAIs) linked with 2,5-diaryl-1,3,4-oxadiazole (OXD) derivatives containing terminal ethynes and butadiyne substituents on the fluorene part of the DHAI skeleton are synthesized via palladium-mediated coupling reaction pathways. Irradiation of the DHAI-OXD derivatives with polychromatic light affords red- and green-colored betaines. (C) 2009 Elsevier Ltd. All rights reserved.