4,4'-bis(CF3(CF2)9CH2OCH2)-2,2'-bipyridine

• 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: 4,4'-bis(CF3(CF2)9CH2OCH2)-2,2'-bipyridine
• 英文别名: 4,4'-bis-(C10F21CH2OCH2)-2,2'-bipyridine；4,4'-(CF3(CF2)9CH2OCH2)-2,2'-bpy；4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Henicosafluoroundecoxymethyl)-2-[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecoxymethyl)pyridin-2-yl]pyridine
• 化学式: C₃₄H₁₄F₄₂N₂O₂
• 分子量: 1280.43
• InChiKey: HSQABOXVNHBKQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.1
• 重原子数：
  80
• 可旋转键数：
  25
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  46

反应信息

• 作为反应物：
  描述：

  4,4'-bis(CF3(CF2)9CH2OCH2)-2,2'-bipyridine 、 双(乙腈)氯化钯(II) 以 二氯甲烷 为溶剂， 以96%的产率得到PdCl₂[4,4'-bis(n-C₁₀F₂₁CH₂OCH₂)-2,2'-bipyridine]
  参考文献：
  名称：

  新型二氯化钯-2,2'-联吡啶与4,4'-双（氟-马尾辫）的合成，结构和反应活性

  摘要：

  摘要利用现成的氟代链烷醇RfCH2OH，制备了一系列新型的氟马尾混合物bpy配体4,4'-bis（RfCH2OCH2）-2,2'-bpy（1a–e），并用[PdCl2（CH3CN）处理）2]生成相应的新型Pd络合物[PdCl2（4,4'-bis（RfCH2OCH2）-2,2'-bpy）]（2a–e），其中Rf = n-C3F7（a），HCF2（CF2 ）3（b），HCF2（CF2）7（c），n-C8F17（d），n-C10F21（e）。通过多核NMR（1H，19F和13C），FTIR和高分辨率质谱（FAB）对新配体和Pd配合物进行了光谱表征。Pd配合物2b的结构，也是通过单晶X射线衍射研究确定的，其第一个在bpy上具有氟化马尾辫，而在膦上不具有氟化马尾辫。配体和Pd配合物的TGA数据表明，Pd配合物比相应的配体具有更高的耐温性。衍生自2a–c的Pd催化剂显示出几乎定量的转化，可通过Heck

  DOI：

  10.1016/j.poly.2007.02.009
• 作为产物：
  描述：

  1H,1H-全氟辛基-1-醇 、 4,4'-双(溴甲基)-2,2'-联吡啶 在 sodium methylate 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以65%的产率得到4,4'-bis(CF3(CF2)9CH2OCH2)-2,2'-bipyridine
  参考文献：
  名称：

  氟双相催化条件下Pd催化的Heck反应的新型双（氟-马尾）联吡啶配体

  摘要：

  三种高度氟化的联吡啶衍生物（4,4'-bis（R f CH 2 OCH 2）-2,2'-bpy）{R f = HCF 2（CF 2）7（1a），n -C 8 F 17（在图1b）中，已经使用4,4'-双（BrCH 2）-2,2'-bpy和相应的氟化醇盐合成了n -C 10 F 21（1c）} 。配体1a – c的氟含量分别为58.3％，59.8和62.3％。尽管氟含量很高，但配体具有-CF 2 H极性末端基团的1a更溶于有机溶剂。配体1b是白色固体，并且仍然适度溶于CH 2 Cl 2中。配体1c具有高的亲氟性，对于n -C 8 F 18 / CH 2 Cl 2系统，分配比为42：1 。配体1a – c与[PdCl 2（CH 3 CN）2 ]的反应产生了新型Pd络合物[PdCl 2（4,4'-bis-（R f CH 2 OCH2）-2,2'-bpy）]，其中R f分别为HCF 2（CF 2）7（2a），n

  DOI：

  10.1016/j.tet.2006.12.053

文献信息

• High Fluorine Content Bis(fluoro-Ponytailed) Bipyridine Palladium Complexes as Catalyst for Mizoroki-Heck Reactions under Fluorous Biphasic Catalysis Conditions
  作者：Norman Lu、Shih-Chieh Chen、Yan-Chou Lin、Yao-Yi Cheng、Ling-Kang Liu

  DOI：10.1002/jccs.200800014

  日期：2008.2

  1:1000. The reaction of ligands la-b with [Pd(CH 3 CN) 2 Cl 2 ] results in novel Pd complexes [PdCl2(4,4'-bis-(R f CH 2 OCH 2 )-2,2'-bpy)] where R f = n-C 10 F 21 (2a), n-C 10 F 23 (2b), respectively. The Pd complexes 2a-b are pale yellow solids, soluble only in fluorinated solvents. The Pd complexes 2a-b have been satisfactorily tested for Mizoroki-Heck arylation under fluorous biphasic catalysis conditions

  两个高度氟化的联吡啶衍生物，(4,4'-bis(R f CH 2 OCH 2 )-2,2'-bpy) R f = nC 10 F 21 (la), nC 10 F 23 (1b)}，已经从 4,4'-bis(BrCH2)-2,2'-bpy 和相应的氟化醇盐开始合成。配体la-b的氟含量分别为62.3%和63.3%，均为白色固体，几乎不溶于CH 2 Cl 2 或DMF，高度亲氟，DMF与nC 8 F 18 的分配比小于1:1000 . 配体 la-b 与 [Pd(CH 3 CN) 2 Cl 2 ] 反应生成新的 Pd 配合物 [PdCl2(4,4'-bis-(R f CH 2 OCH 2 )-2,2'-bpy) ] 其中 R f = nC 10 F 21 (2a), nC 10 F 23 (2b)，分别。Pd 配合物 2a-b 是淡黄色固体，仅溶于氟化溶剂。Pd 配合物 2a-b 在氟双相催化条件下的
• Efficient, recoverable, copper-catalyzed aerobic oxidation of alcohols under FBS and thermomorphic mode
  作者：Norman Lu、Yan-Chou Lin

  DOI：10.1016/j.tetlet.2007.10.074

  日期：2007.12

  successfully used to the aerobic oxidation of alcohols under the fluorous biphasic system (FBS). The resulting products from FBS could be easily recovered by two phase separation with high yields up to 8 runs (>90%). In order to avoid using the expensive fluorous solvents, systems 3a–d, CuBr·Me2S/Bpy (1a–d)/TEMPO, were also successfully shown to catalyze the aerobic alcohol oxidation under the thermomorphic

  一系列氟化联吡啶衍生物，（4,4'-bis（R f CH 2 OCH 2）-2,2'-bpy）R f  =  n -C 8 F 17（1a），n -C 9 F 19（1b），n -C 10 F 21（1c），n -C 11 F 23（1d）}是使用4,4'-双（溴亚甲基）-2,2'-bpy和氟化醇盐成功合成的。Bpy 1a – d已通过多核（1 H，19 F和13 C）NMR，GC / MS和FTIR进行了表征。铜配合物2a – d可以通过在室温下分别将配体1a – d与CuBr·Me 2 S搅拌而原位生成。3组分系统3c - d，CuBr·Me 2 S / Bpy（1c - d）/ 2,2,6,6-四甲基哌啶1-氧基（TEMPO）已成功用于氟双相体系（FBS）下酒精的好氧氧化。通过两相分离可以轻松回收FBS生成的产品，最高收率可达8次（> 90％）。为了避免使用昂贵的氟代溶剂，系统3a
• Recyclable Palladium Catalysts for the Heck/Sonogashira Reaction under Microwave-assisted Thermomorphic Conditions
  作者：Norman Lu、Kwan-Yu Lin、Chieh-Keng Li、Chih-Chieh Kung、Yun-Peng Yeh、Yao-Yi Cheng、Ling-Kang Liu

  DOI：10.1002/jccs.201400252

  日期：2015.1

  cooled, and then the catalysts were recovered by decantation. The Heck arylation catalyzed by 2b under microwave‐assisted mode exhibited good recycling results favoring the trans product. To our knowledge, this is the first example of cationic Pd‐catalyzed Heck arylation under microwave‐assisted thermomorphic conditions. Additionally, recoverable 3b‐catalyzed Sonogashira reactions were also achieved

  在AgOT f存在下，烯丙基氯化钯（II）二聚体与4,4'-双（R f CH 2 OCH 2）-2,2'-bpy，1a–b的反应导致阳离子钯的合成络合物，[将Pd（η 3 -烯丙基）（4,4'-双- （R ˚F CH 2 OCH 2）-2,2'-联吡啶）]（OT ˚F），图2a-b ，其中R ˚F = C 9 ˚F图19（a），C 10 F 21（b）分别表示。[PdCl 2（CH 3 CN）]或K 2的反应具有1b的PdCl 4合成了[bdCl 2（4,4'-bis-（C 10 F 21 CH 2 OCH 2）-2,2'-bpy）] 3b。定量确定的2a–b和3b在DMF中的溶解度曲线表明，从−40到90°C ，2a – b和3b的溶解度急剧增加。在微波辅助下，在DMF中成功地实现了催化剂可回收的Pd催化的Heck / Sonogashira反应。选择了阳离子Pd催化的丙烯酸甲酯Heck
• Recoverable cationic Pd-catalyzed Heck reaction under thermomorphic mode
  作者：Chieh-Keng Li、Ajay Ghalwadkar、Norman Lu

  DOI：10.1016/j.jorganchem.2011.08.028

  日期：2011.11

  The reaction of allylpalladium chloride dimer and 4,4'-bis(RfCH2OCH2)-2,2'-bpy, 1a-c, in the presence of AgOTf resulted in the synthesis of cationic complex, [Pd(eta(3)-allyl)(4,4'-bis-(RfCH2OCH2)-2,2'-bpy)](OTf), 2a-c where R-f = C9F19 (a), C10F21 (b), C11F23 (c), respectively. The solubility curves of 2a-c which began from virtually zero below -40 degrees C and increased dramatically at slightly higher temperature were quantitatively measured. Upon changing from -40-90 degrees C there was several orders of magnitude increase of solubility for 2a-c. The cationic Pd-catalyzed Heck arylation of methyl acrylate was selected to demonstrate the feasibility of recycling usage with 2b,c as the catalyst using DMF as the solvent at 140 degrees C for 3 h in each run. At the end of each cycle, the product mixtures were cooled to -30 degrees C, and then catalysts were recovered by decantation. The products were quantified by GC analysis or by the isolated yield. The Heck reaction of C6H5I with methyl acrylate could be catalyzed by 2b with good recycling results for a total of 15 times and also with a 100% selectivity favoring the trans product. To our knowledge, this is the first example of cationic Pd-catalyzed Heck reaction under the thermomorphic mode. (C) 2011 Elsevier B.V. All rights reserved.
• Efficient, recoverable, copper-free Sonogashira reaction under FBS and thermomorphic mode
  作者：Norman Lu、Yi-Chuan Chen、Wei-Shung Chen、Ter-Lin Chen、Sy-Juen Wu

  DOI：10.1016/j.jorganchem.2008.10.042

  日期：2009.1

  The solubility property of high fluorine content ligands allows us to report in this article the accomplishment under the fluorous biphasic system (FBS) the Pd-catalyzed Sonogashira reactions using novel recyclable Pd catalysts with fluorous-ponytails in the structure of 2,2'-bpy ligands that are only soluble in per fluorinated solvents at room temperature. Alternatively, without using any fluorous solvent but under the thermomorphic mode, the same Pd catalysts proceed with the Cu-free Sonogashira reactions homogeneously in DMF at 135 +/- 5 degrees C, whereas the product mixtures after reaction remain in solution and the Pd catalysts precipitate from DMF at low temperature. (C) 2008 Elsevier B. V. All rights reserved.