N',N'-bis(2-hydroxy-3,5-dimethylbenzyl)-N,N-dimethylethylenediamine

• 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: N',N'-bis(2-hydroxy-3,5-dimethylbenzyl)-N,N-dimethylethylenediamine
• 英文别名: 6,6'-(((2-(dimethylamino)ethyl)azanediyl)bis(methylene))bis(2,4-dimethylphenol)；6,6’-(((2-(dimethylamino)ethyl)azanediyl)bis(methylene))bis(2,4-dimethylphenol)；2-[[2-(Dimethylamino)ethyl-[(2-hydroxy-3,5-dimethylphenyl)methyl]amino]methyl]-4,6-dimethylphenol
• 化学式: C₂₂H₃₂N₂O₂
• 分子量: 356.508
• InChiKey: JLWFPNLDWBBIFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  N',N'-bis(2-hydroxy-3,5-dimethylbenzyl)-N,N-dimethylethylenediamine 以 乙醚 为溶剂， 生成 2,4-ditert-butyl-6-[[(3,5-ditert-butyl-2-oxidophenyl)methyl-propylamino]methyl]phenolate;2-[[2-(dimethylamino)ethyl-[(3,5-dimethyl-2-oxidophenyl)methyl]amino]methyl]-4,6-dimethylphenolate;titanium(4+)
  参考文献：
  名称：

  Coordination Chemistry of Amine Bis(phenolate) Titanium Complexes:  Tuning Complex Type and Structure by Ligand Modification

  摘要：

  The coordination chemistry of titanium(IV) complexes of amine bis(phenolate) ligands was investigated by synthesizing various types of complexes and analyzing them specroscopically and structurally. Steric effects of tridentate [ONO]- and tetradentate [ONNO]-type ligands were studied by reacting the ligand precursors with titanium tetra(isopropoxide). [ONNO]-type ligands featuring an amine donor located on a pendant arm led to octahedral bis(isopropoxide) complexes, regardless of the steric bulk around the metal. Several such complexes having varying steric crowding were thus synthesized. On the other hand, steric effects were found to play a major role in determining the complex constitution when [ONO]-type ligands, featuring no side donor, were involved. Relatively sterically undemanding ligands led to octahedral bis(homoleptic) complexes, whereas increased steric bulk resulted in the formation of pentacoordinate bis(isopropoxide) complexes. These pentacoordinate complexes readily lead to bis(heteroleptic) complexes by reaction with nonsterically demanding [ONO]- and [ONNO]-type ligand precursors. In the latter case the sidearm nitrogen remains uncoordinated to the metal. The bis(isopropoxide) complexes of the [ONNO]-type ligands may also lead to bis(heteroleptic) complexes, however, these reactions are much slower.

  DOI：

  10.1021/ic010210s
• 作为产物：
  描述：

  在 水 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 N',N'-bis(2-hydroxy-3,5-dimethylbenzyl)-N,N-dimethylethylenediamine
  参考文献：
  名称：

  [ONON]型钛（IV）双螯合物在醇溶剂中的简易合成及抗肿瘤活性评价

  摘要：

  通过使用正丙醇作为溶剂并使用 H 2 O 进行分离的高效方案，合成了由 2,6-吡啶二羧酸稳定的新型抗肿瘤二氨基-双-（苯酚）[ONON] 型钛(IV)配合物。总共合成了 20 种 [ONON] 型和 2 种 Salan Ti (IV)双螯合配合物，产率从 68% 到 96%。使用 Ti(O i Pr) 4或 TiCl 4作为起始材料，所有反应都可以在 80 °C 的 1.5 分钟内完成。与 Salan Ti 相比，大多数 [ONON] 型 Ti (IV)复合物对 Hep G2 细胞表现出选择性增强的抑制活性 （四）配合物。其中，2t (IC 50 : 0.15 ± 0.1 μM)对Hep G2细胞的抑制活性比 顺铂( IC 50 : 12.4 ± 1.2 μM)增强约80倍。[ONON] 型 Ti (IV)配合物在存在大量水性介质的情况下缓慢释放无毒的酚酸配体，并且基于金属摄取分析提出了这些

  DOI：

  10.1016/j.jinorgbio.2022.111925

文献信息

• Zirconium complexes stabilized by amine-bridged bis(phenolato) ligands as precatalysts for intermolecular hydroamination reactions
  作者：Qiu Sun、Yaorong Wang、Dan Yuan、Yingming Yao、Qi Shen

  DOI：10.1039/c5dt02643a

  日期：——

  Pentacoordinate zirconium complexes 5 and 7 stabilized by amine-bridged bis(phenolato) ligands are more active than hexacoordinate complexes 1–4 in catalyzing intermolecular hydroamination reactions.

  由胺桥联的双(酚ato)配体稳定的五配位锆配合物 5 和 7 比六配位的配合物 1–4 在催化分子间氢氨化反应时更为活跃。

• Scorpionate Catalysts for Coupling CO₂ and Epoxides to Cyclic Carbonates: A Rational Design Approach for Organocatalysts
  作者：Mannkyu Hong、Yoseph Kim、Hyejin Kim、Hee Jin Cho、Mu-Hyun Baik、Youngjo Kim

  DOI：10.1021/acs.joc.8b00722

  日期：2018.8.17

  Novel scorpionate-type organocatalysts capable of effectively coupling carbon dioxide and epoxides under mild conditions to afford cyclic propylene carbonates were developed. On the basis of a combined experimental and computational study, a precise mechanistic proposal was developed and rational optimization strategies were identified. The epoxide ring-opening, which requires an iodide as a nucleophile

  开发了能够在温和条件下有效偶联二氧化碳和环氧化物以提供环状碳酸亚丙酯的新型蝎子型有机催化剂。在实验和计算研究相结合的基础上，提出了一种精确的机械方案，并确定了合理的优化策略。通过利用可以与碘化物形成离子对的铵官能团，使需要碘化物作为亲核试剂的环氧开环反应得以增强，从而使开环过程成为分子内的。一氧化碳2活化和环状碳酸酯的形成是由两个氢键的协同作用催化的，该氢键源自放置在蝎形支架爪位置的两个酚基。氢键供体的电子调节可以确定一种新型催化剂，该新型催化剂在室温下仅10 bar的CO 2压力下，在7小时内可为多种环氧底物提供> 90％的产率，并且具有很高的可回收性。
• Reaction of CO₂with a Vanadium(II) Aryl Oxide: Synergistic Activation of CO₂/Oxo Groups towards H-Atom Radical Abstraction
  作者：Camilo J. Viasus、Nicholas P. Alderman、Bulat Gabidullin、Sandro Gambarotta

  DOI：10.1002/anie.201805569

  日期：2018.8.20

  formate groups both originated from CO2, the H atoms present on the two residues were obtained through H‐atom radical abstraction from the solvent. DFT calculations revealed an initially linear CO2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the so‐formed oxo group and an additional bridging CO2 residue in promoting radical behavior.

  二价的治疗（ONNO）V（TMEDA）（1 ; ONNO = [2,4-ME 2 -2-（OH）C 6 H ^ 2 CH 2 ] 2 N（CH 2）2 NME 2）用CO 2，得到[ （ONNO）V] 2（μ-OH）（μ-甲酸酯）（2）。桥连的羟基和甲酸酯基团均起源于CO 2，两个残基上存在的H原子是通过从溶剂中提取H原子自由基获得的。DFT计算显示出最初呈线性的CO 2键模式，然后进行脱氧，并强调了形成的羰基与额外的桥接CO 2残基之间在促进自由基行为方面的协同作用。
• Dioxidomolybdenum(VI) and –tungsten(VI) complexes with tetradentate amino bisphenolates as catalysts for epoxidation
  作者：Jörg A. Schachner、Nadia C. Mösch-Zanetti、Anssi Peuronen、Ari Lehtonen

  DOI：10.1016/j.poly.2017.06.011

  日期：2017.9

  Abstract Sixteen molybdenum and tungsten complexes with tripodal or linear tetradentate amino bisphenol ligands were studied as catalysts for the epoxidation of cis-cyclooctene, 1-octene, styrene, limonene and α-terpineol. These complexes can be divided into different categories upon key features, i.e. central metal (Mo versus W), side-arm donor (O versus N), hybridization of the N-donor (pyridine

  摘要研究了十六个具有三脚或线性四齿氨基双酚配体的钼和钨配合物，作为顺式环辛烯，1-辛烯，苯乙烯，柠檬烯和α-萜品醇的环氧化催化剂。这些复合物可根据主要特征分为不同类别，即中心金属（Mo与W），侧臂供体（O与N），N供体的杂交（吡啶与胺），配体几何形状（三脚架与线性二胺） ）和空间位阻（苯酚部分中的Me与叔丁基取代基）。所有的配合物都可以选择性地催化叔丁基过氧化氢对顺式环辛烯的环氧化，而对其他烯烃（1-辛烯，苯乙烯，mon烯和α-松油醇）的活性和选择性则表现出很大的差异。当H2O2在顺式环辛烯的环氧化中用作氧化剂时，八个Mo络合物中只有两个和八个W络合物中的四个显示出任何活性。这项研究表明Mo和W催化剂结构与其活性之间没有明确的相关性。
• Ethylene Homo‐ and Copolymerization Activity of a Series of [ONNO]‐Type Amine Bis(phenolate) Based Vanadium( <scp>II</scp> – <scp>V</scp> ) Catalysts
  作者：Christian Lorber、Fabien Wolff、Robert Choukroun、Laure Vendier

  DOI：10.1002/ejic.200500149

  日期：2005.7

  synthesis and structural characterization of new paramagnetic amine bis(phenolate) [ONNO]-vanadium(III) and-vanadium(II) complexes, VIII(acac)[ONNO], VIII(Cl)(THF)[ONNO], and VII(TMEDA)[ONNO], is described. These compounds complete the family of [ONNO]-vanadium(IV/V) complexes previously reported. The members of the [ONNO]-vanadium family at various oxidation states that range from vanadium(II) to vanadium(V)

  新型顺磁性胺双(苯酚)[ONNO]-钒(III)和-钒(II)配合物、VIII(acac)[ONNO]、VIII(Cl)(THF)[ONNO]和VII的合成和结构表征(TMEDA)[ONNO]，进行了描述。这些化合物完善了先前报道的 [ONNO]-钒 (IV/V) 配合物家族。在乙烯聚合和乙烯-1-己烯的共聚中，研究了 [ONNO]-钒家族成员在从钒 (II) 到钒 (V) 的各种氧化态下，与 EtAlCl2 助催化剂结合和乙烯-降冰片烯。聚（乙烯-共-1-己烯）和聚（乙烯-共-降冰片烯）的共聚单体含量分别高达 11 mol-% 和 29 mol-%，1-己烯和降冰片烯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)