6,6′-(2-(pyridin-2-yl)ethylazanediyl)bis(methylene)bis(2,4-ditert-butylphenol) | 354160-03-5

• 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: 6,6′-(2-(pyridin-2-yl)ethylazanediyl)bis(methylene)bis(2,4-ditert-butylphenol)
• 英文别名: 2,4-Ditert-butyl-6-[[(3,5-ditert-butyl-2-hydroxyphenyl)methyl-(2-pyridin-2-ylethyl)amino]methyl]phenol；2,4-ditert-butyl-6-[[(3,5-ditert-butyl-2-hydroxyphenyl)methyl-(2-pyridin-2-ylethyl)amino]methyl]phenol
• CAS: 354160-03-5
• 化学式: C₃₇H₅₄N₂O₂
• 分子量: 558.848
• InChiKey: ROWLQLOZIXVVCQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  56.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(acetylacetonate)oxovanadium 、 6,6′-(2-(pyridin-2-yl)ethylazanediyl)bis(methylene)bis(2,4-ditert-butylphenol) 在 TEA 作用下， 以 乙腈 为溶剂， 反应 3.17h， 以70%的产率得到
  参考文献：
  名称：

  N 2 O 2供体胺双（酚盐）配体与溴过氧化物酶活性的两种双核氧钒（V）配合物：动力学，催化和计算研究

  摘要：

  摘要两个ONNO供体胺-双（​​酚盐）配体的两个双核氧钒（V）络合物[LiVVO（µ2-O）VVO（Li）]（i = 1，H2L1，络合物1，i = 2，H2L2，络合物2）通过X射线衍射研究合成并表征了X射线衍射研究，该研究在每个V中心周围显示了扭曲的八面体几何形状。在MeCN中，如HRMS研究所示，络合物以二聚体形式存在，但是，在存在2个或更多当量的H +时，二聚体转变为单体，（[LiVV = O] +与（[LiVV = OH] 2 +并从复合物1的λmax从685 nm到765 nm和复合物2的600到765 nm的位移证明。复合物1和2在H2O2存在下有效催化水杨醛的氧化溴化反应，生成5-溴-水杨醛作为TON 405和450的主要产品，分别在混合溶剂系统中（H2O：MeOH：THF = 4：3：2，v / v）。溴离子氧化反应的动力学分析表明了一种机理，该机理在过氧化物钒络合物和溴离子中是一级的，并且在[H

  DOI：

  10.1016/j.ica.2018.04.044
• 作为产物：
  描述：

  2-(2-氨乙基)吡啶 、 2,4-二叔丁基苯酚 以 甲醇 为溶剂， 反应 12.0h， 以47%的产率得到6,6′-(2-(pyridin-2-yl)ethylazanediyl)bis(methylene)bis(2,4-ditert-butylphenol)
  参考文献：
  名称：

  三脚架配体的 钒（v）配合物，其表征和生物学意义†

  摘要：

  三脚架四齿二元配体6,6'-（2-（吡啶-2-基）乙基氮杂二基）双（亚甲基）双（2,4-二叔丁基苯酚）H 2 L 1 I与[ CH 3 CN中的V IV O（acac）2 ]给出V V O-络合物[V V O（acac）（L 1）] 1。结晶1在CH 3 CN在约0℃下给出了深蓝色晶体1，同时在室温下它可以提供[{V的深绿色结晶V 0（1 1）} 2 μ-O] 3。长期治疗在MeOH中为1，获得[V V O（OMe）（MeOH）（L 1）] 2。通过单晶X射线衍射分析了所有三种配合物，描绘了钒周围扭曲的八面体几何形状。在H 2 L 1与V IV OSO 4的反应中，三脚架配体的部分水解可消除L 1的吡啶基片段，并形成含有ONO三齿形的H [V V O 2（L 2）] 4。配体6,6'-氮杂二基双（亚甲基）双（2,4-二叔丁基苯酚），H 2 L 2二。化合物4，这是不完全表征，经历二聚化在丙酮得到的hydroxido桥连[{V

  DOI：

  10.1039/c5dt02716k

文献信息

• Dioxomolybdenum(VI) complexes with linear and tripodal tetradenate ligands: Synthesis, structures and their use as olefin epoxidation catalysts
  作者：Xiangyang Lei、Nagasree Chelamalla

  DOI：10.1016/j.poly.2012.10.022

  日期：2013.1

  Abstract A series of linear and tripodal tetradentate ligands containing an amine-bis(phenolate) core were synthesized by Mannich condensations. Treatment of these ligands with MoO2(acac)2 (acac = acetylacetonate) in dichloromethane and methanol at room temperature gave the corresponding cis-dioxomolybdenum(VI) complexes in good yields. All these complexes were characterized by a wide range of spectroscopic

  摘要通过曼尼希缩合反应，合成了一系列含有胺-双（酚盐）核的线性和三脚形四齿配体。在室温下在二氯甲烷和甲醇中用MoO2（acac）2（acac =乙酰丙酮化物）处理这些配体，得到相应的顺式-二氧钼（VI）配合物，收率很高。所有这些复合物的特征均来自多种光谱方法（NMR，IR和UV-Vis）和元素分析。MoO2（Ln）（n = 1-3，5）的配合物的分子结构已通过单晶X射线衍射分析确定。还研究了所有络合物对叔丁基过氧化氢对苯乙烯环氧化的催化活性。
• Solvent Dependent Disproportionation of Cu(II) Complexes of N2O2-Type Ligands: Direct Evidence of Formation of Phenoxyl Radical: An Experimental and Computational Study
  作者：Rajib Kumar Debnath、Apurba Kalita、Sourab Sinha、Pradip Kr. Bhattacharyya、Biplab Mondal、Jatindra Nath Ganguli

  DOI：10.14233/ajchem.2015.19193

  日期：——

  Four Cu(II) complexes (1, 2, 3 and 4) with N2O2-type ligand, H2L1, H2L2, H2L3 and H2L4, respectively have been synthesized as the functional model for galactose oxidase. In presence of acetonitrile the Cu(II) centres in the complexes, undergo reduction with simultaneous oxidation of the ligands. The ligand oxidized products are isolated and characterized. Spectroscopic studies indicate that this disproportionation goes through the formation of a Cu(II)-phenoxyl intermediate. The complexes also undergoes the same reaction with pyridine, which indicates the involvement of the exergonic N-donor ligand for the formation of Cu(II)-phenoxyl complex. The Cu(II)-phenoxyl complexes are found to be stable in methanol in presence of a strong base. The paramagnetic centers in the Cu(II)-phenoxyl complexes were found to be weakly ferromagnetically coupled. The complexes, in acetonitrile solvent, have been found to oxidize primary alcohols to corresponding aldehydes. In absence of single crystal structures of the complexes, we optimized the structures using density functional theory (DFT). The UV-visible peaks of complexes as found from time dependent density functional theory (TDDFT) calculations match well with the observed experimental results.

  合成了四种Cu(II)络合物（1, 2, 3和4），其配体为N2O2型的H2L1、H2L2、H2L3和H2L4，作为乳糖氧化酶的功能模型。在乙腈存在下，络合物中的Cu(II)中心发生还原，同时配体被氧化。氧化的配体产物被分离并进行表征。光谱研究表明，这一不均化反应是通过形成Cu(II)-苯氧基中间体进行的。这些络合物在吡啶存在下也发生同样反应，表明外能量N-供体配体参与了Cu(II)-苯氧基络合物的形成。Cu(II)-苯氧基络合物在强碱存在下在甲醇中被发现是稳定的。Cu(II)-苯氧基络合物中的顺磁中心被发现弱耦合成铁磁性。在乙腈溶剂中，这些络合物能够将初级醇氧化为相应的醛。在缺乏单晶结构的情况下，我们使用密度泛函理论（DFT）对其结构进行了优化。从时间相关密度泛函理论（TDDFT）计算中获得的络合物的紫外-可见光谱峰与观察到的实验结果良好匹配。
• [ONNO]-type oxovanadium(V) complexes containing amine pyridine bis(phenolate) ligands: synthesis, characterization and catalytic behavior for ethylene (co)polymerization
  作者：Jia-Bao Wang、Ling-Pan Lu、Jing-Yu Liu、Hong-liang Mu、Yue-Sheng Li

  DOI：10.1016/j.molcata.2014.12.016

  日期：2015.3

  molecular weight distributions, indicative of a single active site nature. In addition, copolymerizations of ethylene and norbornene using precatalysts 2a–e were also investigated, and the observed catalytic activity was nearly comparable with that for ethylene homopolymerization. When the concentration of comonomer in the feed amounted to 3.0 mol/L, a NBE incorporation up to 41.5% could be achieved.

  一系列带有阴离子[ONNO]螯合配体2- [双（3-R 1 -5-R 2 -2-羟基苄基）氨基甲基]吡啶的氧钒（V）络合物（2a：R 1  =  t Bu，R 2  = H ；2b：R 1  ＝ CF 3，R 2  ＝ H；2c：R 1  ＝ OCH 3，R 2  ＝ H；2d：R 1  ＝ R 2  ＝  t Bu）和2- [bis（3-R 1 -5） -R 2 -2-羟基苄基）氨基乙基]吡啶（2e：R 1通过使VO（O n Pr）3与1.0当量反应合成了 ＝ R 2  ＝  t Bu）。CH 2 Cl 2中的配体的数目。所有这些配合物均通过1 H，13 C，51 V NMR光谱和元素分析表征。二维的X射线结构分析显示，固态时钒中心周围六坐标扭曲的八面体几何形状。观察到这些络合物以两种异构体的混合物形式存在，并且主要异构体具有与三脚架氮原子反式构型的氧代部分。在Et 2 AlCl和CCl存在下3
• 一种金属有机发光钨配合物及其合成方法
  申请人：天津大学

  公开号：CN110204578B

  公开（公告）日：2021-09-28

  本发明公开了一种金属有机钨配合物及其合成方法，主要是用1倍物质的量的2,4‑二取代苯酚亚胺类化合物和1倍物质的量的二氯二氧化钨和1:2.1至1:2.2倍物质的量的吡啶，以甲苯为溶剂，在115℃至120℃的条件下回流反应至少24小时，得到金属有机钨配合物，并对其紫外吸收光谱和荧光发射光谱进行研究，紫外最大吸收波长位于260nm左右，最大荧光发射光谱位于285nm左右。本发明合成的金属钨配合物可作为有机发光二极管的发光层。同时，为研究该类化合物的性质和应用提供了依据。
• Zirconium Complexes of Amine−Bis(phenolate) Ligands as Catalysts for 1-Hexene Polymerization:  Peripheral Structural Parameters Strongly Affect Reactivity
  作者：Edit Y. Tshuva、Israel Goldberg、Moshe Kol、Zeev Goldschmidt

  DOI：10.1021/om0101285

  日期：2001.7.1

  Novel amine bis(phenolate) zirconium dibenzyl complexes were synthesized in quantitative yields from a versatile family of chelating amine -bis((2-hydroxyaryl)methyl) ligand precursors, their X-ray structures solved, and their reactivity in the polymerization of l-hexene in the presence of B(C6F5)(3) studied. Several minor peripheral structural modifications were studied and found to have a major influence on the catalyst performance. Thus, a variety of reactivities, ranging from extremely high to negligible, were obtained, demonstrating a unique structure-reactivity relationship. This relationship is partially revealed from the crystal structures of the precatalysts, indicating similar [ONO] ligand cores in all structures solved. A correlation between the solid and the solution structures is obtained from H-1 NMR spectra, which reveal a rigid binding of the ligand to the metal. The solid structures are therefore proposed to serve as reliable references when studying structure-reactivity relationships. The most significant structural parameter was found to be the existence of an extra donor located on a pendant arm. [ONO]-type pentacoordinate complexes lacking such an additional donor are rapidly deactivated and lead only to traces of oligomers. On the other hand, hexacoordinate complexes based on [ONNO]-type ligands, in which strong donation of a side donor to the metal is obtained through formation of a five-membered chelate, lead to extremely reactive polymerization catalysts. The nitrogen hybridization and aromatic ring substituents have a more subtle effect on reactivity. Increasing the chelate size results in either no binding of the side donor, yielding negligible reactivity, or strong binding yet moderate polymerization reactivity. Increasing the steric bulk on the donor results in weakening of the metal-donor bond, leading to a moderate oligomerization catalyst. The sidearm nitrogen is therefore proposed to play a crucial role in determining the propagation process rate, as well as the propagation/termination rate ratio.