(6,6-(((2-(diethylamino)ethyl)azanediyl)bis(methylene))bis(methylene))bis(2,4-dimethylphenol) | 354160-05-7

• 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-(diethylamino)ethyl)azanediyl)bis(methylene))bis(methylene))bis(2,4-dimethylphenol)
• 英文别名: N,N-bis(3,5-dimethyl-2-hydroxybenzyl)-N’,N’-diethyl-1,2-diaminoethane；2,2'-[{[2-(diethylamino)ethyl]imino}bis(methylene)]bis[4,6-dimethylphenol]；6,6'-(((2-(diethylamino)ethyl)azanediyl)bis(methylene))bis(2,4-dimethylphenol)；Et2NCH2CH2N(CH2-6-C6H2(OH)Me2-2,4)2；2-[[2-(Diethylamino)ethyl-[(2-hydroxy-3,5-dimethylphenyl)methyl]amino]methyl]-4,6-dimethylphenol
• CAS: 354160-05-7
• 化学式: C₂₄H₃₆N₂O₂
• 分子量: 384.562
• InChiKey: IFJJZJHSKCFCHU-UHFFFAOYSA-N

物化性质

• 沸点：
  493.7±40.0 °C(Predicted)
• 密度：
  1.072±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (6,6-(((2-(diethylamino)ethyl)azanediyl)bis(methylene))bis(methylene))bis(2,4-dimethylphenol) 、 四苄基锆 以 甲苯 为溶剂， 以30%的产率得到
  参考文献：
  名称：

  Zirconium Complexes of Amine−Bis(phenolate) Ligands as Catalysts for 1-Hexene Polymerization:  Peripheral Structural Parameters Strongly Affect Reactivity

  摘要：

  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.

  DOI：

  10.1021/om0101285
• 作为产物：
  描述：

  聚合甲醛 、 2,4-二甲基苯酚 在 N,N-二乙基乙二胺 作用下， 以 甲醇 为溶剂， 以45.76 %的产率得到(6,6-(((2-(diethylamino)ethyl)azanediyl)bis(methylene))bis(methylene))bis(2,4-dimethylphenol)
  参考文献：
  名称：

  水解稳定性和细胞毒性 [ONON]2Ti(IV) 型八面体配合物

  摘要：

  合成并表征了基于具有 Me、Br、Cl 和 F 邻位取代的 [ONON] 二氨基双（苯酚）配体的新钛 (IV) 配合物家族。三种衍生物的 X 射线结构揭示了均配 L 2 Ti 型化合物，这些化合物具有八面体几何结构，没有悬空胺单元的结合。DFT 计算表明 L 2的偏好Ti 络合物不是由溶剂或配体取代驱动，而是由熵效应驱动。除了氟化衍生物在室温下加水后立即水解并且在所测试的系列中具有最低的生物活性外，所有其他复合物对人卵巢的细胞毒性活性与顺铂相当或更高（高达 10 倍） A2780 和结肠 HT-29 癌细胞系 (IC 50值：孵育 72 小时后为 0.6–13 μM）。对更敏感的卵巢线的活性通常更高（高达 10 倍）并且所有活性复合物的活性相似，而记录到结肠线的差异归因于所分析的复合物之间的生物利用度变化。溴化衍生物的水解稳定性特别高，配体在 10% D 2 O 中室温水解的t 1/2为 17

  DOI：

  10.1021/acs.inorgchem.2c02737

文献信息

• Accelerated syntheses of amine-bis(phenol) ligands in polyethylene glycol or “on water” under microwave irradiation
  作者：Francesca M Kerton、Stacey Holloway、Angela Power、R Graeme Soper、Kristina Sheridan、Jason M Lynam、Adrian C Whitwood、Charlotte E Willans

  DOI：10.1139/v08-043

  日期：2008.5.1

  Pure amine-bis(phenol) ligands are readily accessible in high yield, often >90%, when the Mannich condensation reactions are performed “on water” or in poly(ethyleneglycol) (PEG). Microwave-assisted synthesis dramatically reduces the time and energy required to prepare these molecules, typically from 24 h to 5 min. The approach seems to be widely applicable (7 amines and 5 phenols were tested to yield a diverse set of bis(phenol) ligands). Significant improvements in yield were observed for ligands derived from di-tert-amyl and di-tert-butyl phenols, possibly resulting from a hydrophobic effect. Single crystal X-ray diffraction data for the ligand derived from p-cresol and N,N′-dimethylethylenediamine is reported.Key words: amine-phenol, Mannich condensation, on water, microwave, ligand, high-throughput.

  当曼尼希缩合反应在 "水上 "或聚（乙二醇）（PEG）中进行时，很容易获得纯胺-双（酚）配体，而且收率很高，通常可达 90%。微波辅助合成大大减少了制备这些分子所需的时间和能量，通常可从 24 小时缩短到 5 分钟。这种方法似乎具有广泛的适用性（对 7 种胺和 5 种酚进行了测试，得到了多种双（酚）配体）。从二叔戊基苯酚和二叔丁基苯酚衍生出的配体的产率显著提高，这可能是疏水效应的结果。报告了由对甲酚和 N,N′-二甲基乙二胺衍生的配体的单晶 X 射线衍射数据。 关键词：胺-酚、曼尼希缩合、水、微波、配体、高通量。
• Synthesis and characterization of new divalent lanthanide complexes supported by amine bis(phenolate) ligands and their applications in the ring opening polymerization of cyclic esters
  作者：Divine T. Dugah、Brian W. Skelton、Ewan E. Delbridge

  DOI：10.1039/b816916k

  日期：——

  A selection of divalent compounds (1, 3, 4, 5, 6 and 7) were tested as catalyst precursors in the polymerization of ε-caprolactone and/or L-lactide which resulted in high molecular weight polymers with PDIs of 1.11–2.81 and 1.13–1.56 for ε-caprolactone and L-lactide respectively. All polymerization studies were performed in either toluene or THF and at room temperature (ε-caprolactone) or 70 °C (L-lactide)

  二阵列的处理（酚）中文2大号X L X = [（- OC 6 H ^ 2（2,4-R）（6-CH 2））2 NCH 2 CH 2 X]，其中X = CH 2 NMe 2，NMe 2，NEt 2，OMe，R = Bu t，Pe t，其中Pe t = C（CH 3）2 Et}与[Ln（N（SiMe 3）2）2（THF）2]（Ln为镱，钐）以1：在己烷中，得到的新的二价镧系元素的双（酚盐）复合物的大量1的摩尔比：[L 2C的Yb] 2（X = NET 2，R =卜吨）1，[ L 2b Yb] 2（X = CH 2 NMe 2，R = Bu t）2，[L 3a Yb] 2（X = NMe 2，R = Pe t）3，[L 3b Yb] 2（X = OMe， R = Pe t）4，[L 2c Sm]（X = NEt 2，R = Bu t）5，[L 3c Yb]（X = NEt 2，R = Pe t）6，[L
• Synthesis and structure of amine-bridged bis(phenolate) lanthanide complexes and their application in the polymerization of ε-caprolactone
  作者：Le-Qing Deng、Yan-Xu Zhou、Xian Tao、Yu-Long Wang、Qing-Song Hu、Pan Jin、Ying-Zhong Shen

  DOI：10.1016/j.jorganchem.2013.10.031

  日期：2014.1

  (Ln = La, Gd). The bis(phenolate) lanthanide amides L1–6La[N(SiMe3)2] (1–6) were given by the reactions of La[N(SiMe3)2]3 with H2L1–6 in 1:1 M ration in THF. The bis(phenolate) lanthanide complexes Ln2[L6]3 (Ln = La (7), Ln = Gd (8)) were given by the reactions of Ln[N(SiMe3)2]3(Ln = La, Ga) with H2L6 in 2:3 M ratio in THF. Complexes 3 and 8 have been characterized by X-ray crystal structural analysis. The

  一系列镧系络合物的1 - 8通过胺桥连的双胺消去反应（酚），得到ħ 2大号1 - 3 [大号1 - 3  =的Et 2 NCH 2 CH 2 N CH 2 - （2-O- -C 6 H 2 -R 2 -3-R 1 -5）2，R 1  ＝  t Bu，R 2  ＝  t Bu（L 1）；R 1  =我，R 2  = t Bu（ L 2）; R 1  = Me，R 2  = Me（ L 3）]和H 2 L 4 – 6 [ L 4 – 6  = CH 3 CH 2 CH 2 N CH 2 –（2-O–C 6 H 2 –R 2 -3–R 1 -5）} 2，R 1  ＝  t Bu，R 2  ＝  t Bu（ L 4）；R 1  =我，R 2 ＝  t Bu（L 5）；R 1  ＝ Me，R 2  ＝ Me（L 6）]，其中Ln [N（SiMe 3）2 ] 3（Ln ＝ La，Gd）。通过La [N（SiMe
• Synthesis, characterization and phosphotriesterase mimetic activity of some Zn(II) and Cu(II) complexes
  作者：MAMATA SINGH、RAY J BUTCHER、JERRY P JASINSKI、JAMES A GOLEN、GOVINDASAMY MUGESH

  DOI：10.1007/s12039-012-0331-4

  日期：2012.11

  the synthesis and characterization of a few phenolate-based ligands bearing tert- amino substituent and their Zn(II) and Cu(II) metal complexes. Three mono/binuclear Zn(II) and Cu(II) complexes [Zn(L1)(H2O)].CH3OH.H2O (1) (H 2 L1 = 6,6′-(((2-dimethylamino)ethylazanediyl)bis(methylene))bis(2, 4-dimethylphenol), [Zn2(L2)2] (2) (H 2 L2 = 2,2′-(((2-dimethylamino)ethyl)azanediyl)bis(methylene)bis(4- methylphenol)

  我们在这里报告了一些带有叔氨基取代基的酚盐基配体及其Zn（II）和Cu（II）金属配合物的合成和表征。三种单/双核Zn（II）和Cu（II）配合物[Zn（L1）（H 2 O）]。CH 3 OH.H 2 O （1）（H 2 L1 = 6,6 ′ -（（（2 -（二甲基氨基）乙基氮杂二基）双（亚甲基））双（2，4-二甲基苯酚），[Zn 2（L2）2 ] （2）（H 2 L2 = 2,2 ' -（（（（2-二甲基氨基）乙基）氮杂二基）二（亚甲基）二 （4-甲基苯酚）和[Cu 2（L3）2 .CH 2 Cl 2 ] （3）（H 2 L3 =（6,6 ' -（（（（2-（二乙基氨基）乙基）氮杂二基）双（亚甲基））双（亚甲基）双（2,4-二甲基苯酚）是通过使用三个对称的含有N 2 O 2供体位点的对称四齿碳酸盐配体合成的，这些络合物通过多种技术进行表征，包括元素分析，质谱，1 H，13 C NMR光谱和单晶X射线分析。借助31
• Mixed azido/phenoxido bridged trinuclear Cu(<scp>ii</scp>) complexes of Mannich bases: Synthesis, structures, magnetic properties and catalytic oxidase activities
  作者：Avijit Das、Kisholoy Bhattacharya、Lakshmi Kanta Das、Sanjib Giri、Ashutosh Ghosh

  DOI：10.1039/c8dt01400k

  日期：——

  all three complexes, the central Cu(ii) ion is coordinated by two terminal [CuL] units through a phenoxido and an azido bridge. These are the first trinuclear Cu(ii) complexes of this type of Mannich base ligands. Magnetic susceptibility measurements showed intramolecular antiferromagnetic interactions with J = -64.42, -9.60 and -4.54 cm-1 for 1, 2 and 3, respectively. All three complexes exhibited

  三种相似的曼尼希碱基配体。N，N-双（3,5-二甲基-2-羟基苄基）-N'，N'-二甲基-1,3-二氨基丙烷（H2L1），N，N-双（3,5-二甲基-2-羟基苄基） -N'，N'-二甲基-1,2-二氨基乙烷（H2L2）和N，N-双（3,5-二甲基-2-羟基苄基）-N'，N'-二乙基-1,2-二氨基乙烷（H2L3 ）与Cu（CH3COO）2·H2O反应生成双核配合物[Cu2L21-3]。这些分离的二聚体每种与Cu（ClO4）2·6H2O和NaN3的反应产生了三个新的三核络合物[[CuL1）2（μ1,1-N3）2Cu（H2O）]·CH3OH（1），[ （CuL2）2（μ1,1-N3）2Cu（H2O）]·CH3OH（2）和[（CuL3）2（μ1,1-N3）2Cu（H2O）]·2CH3OH（3）。配合物（1-3）已经通过元素分析和单晶X射线衍射表征。在所有三个复合体中，中心的Cu（ii）离子通过苯