3,4-dibutyl-2,5-bis[(5'-ethynyl-2,2'-bipyridin-5-yl)ethynyl]thiophene | 794529-30-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3,4-dibutyl-2,5-bis[(5'-ethynyl-2,2'-bipyridin-5-yl)ethynyl]thiophene
• 英文别名: 2-[5-[2-[3,4-Dibutyl-5-[2-[6-(5-ethynylpyridin-2-yl)pyridin-3-yl]ethynyl]thiophen-2-yl]ethynyl]pyridin-2-yl]-5-ethynylpyridine；2-[5-[2-[3,4-dibutyl-5-[2-[6-(5-ethynylpyridin-2-yl)pyridin-3-yl]ethynyl]thiophen-2-yl]ethynyl]pyridin-2-yl]-5-ethynylpyridine
• CAS: 794529-30-9
• 化学式: C₄₀H₃₂N₄S
• 分子量: 600.787
• InChiKey: KIDCSFRITMPCKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  79.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-[(3,4-dibutyl-5-iodothien-2-yl)ethynyl]-5'-(triethylsilyl)ethynyl-2,2'-bipyridine 、 3,4-dibutyl-2,5-bis[(5'-ethynyl-2,2'-bipyridin-5-yl)ethynyl]thiophene 在 四(三苯基膦)钯 三乙胺 作用下， 以 苯 为溶剂， 以87%的产率得到3,4-dibutyl-2,5-bis[(5'-{[3,4-dibutyl-5-({5'-[(triethylsilyl)ethynyl]-2,2'-bipyridin-5-yl}ethynyl)thien-2-yl]ethynyl}-2,2'-bipyridin-5-yl)ethynyl]thiophene
  参考文献：
  名称：

  Oligomeric Ligands Incorporating Multiple 5,5‘-Diethynyl-2,2‘-bipyridine Moieties Bridged and End-Capped by 3,4-Dibutylthiophene Units

  摘要：

  In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)(2)C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to hipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and endcapped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.

  DOI：

  10.1021/jo048435i
• 作为产物：
  描述：

  5,5'-二溴-2,2'-联吡啶 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四(三苯基膦)钯 sodium hydroxide 、 potassium carbonate 、 三乙胺 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 、 苯 为溶剂， 反应 9.0h， 生成 3,4-dibutyl-2,5-bis[(5'-ethynyl-2,2'-bipyridin-5-yl)ethynyl]thiophene
  参考文献：
  名称：

  Oligomeric Ligands Incorporating Multiple 5,5‘-Diethynyl-2,2‘-bipyridine Moieties Bridged and End-Capped by 3,4-Dibutylthiophene Units

  摘要：

  In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)(2)C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to hipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and endcapped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.

  DOI：

  10.1021/jo048435i

文献信息

• A convenient method of producing thiophene linked bipyridine oligomers
  作者：Antoinette De Nicola、Sébastien Goeb、Raymond Ziessel

  DOI：10.1016/j.tetlet.2004.08.062

  日期：2004.10

  A series of soluble polybipyridine ligands comprising one to five bipyridine modules sandwiched between rigid carboncarbon triple bonds substituted by 3,4-dibutylthiophene repeating units was synthesized. Two different protocols have been explored with the idea to use a divergent/convergent approach starting from bisymmetrically and symmetrically substituted bipyridine modules. At each stage of the iteration two bipy/thiophene modules are connected. The use of triethylsilylacetylene and 2-methylbut-3-yn-2-ol insures an easy entry to pivotal building blocks, which could be selectively deprotected from the TES or 2-hydroxyprop-2-yl sites. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. (C) 2004 Elsevier Ltd. All rights reserved.
• Oligomeric Ligands Incorporating Multiple 5,5‘-Diethynyl-2,2‘-bipyridine Moieties Bridged and End-Capped by 3,4-Dibutylthiophene Units
  作者：Sébastien Goeb、Antoinette De Nicola、Raymond Ziessel

  DOI：10.1021/jo048435i

  日期：2005.3.1

  In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)(2)C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to hipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and endcapped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.