benzylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol) | 1033003-01-8

• 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: benzylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol)
• 英文别名: 6,6'-((benzylazanediyl)bis(methylene))bis(2,4-di-tert-butylphenol)；2-[[Benzyl-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]amino]methyl]-4,6-ditert-butylphenol；2-[[benzyl-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]amino]methyl]-4,6-ditert-butylphenol
• CAS: 1033003-01-8
• 化学式: C₃₇H₅₃NO₂
• 分子量: 543.833
• InChiKey: WPGXLZRDLVFEMC-UHFFFAOYSA-N

物化性质

• 沸点：
  564.9±45.0 °C(Predicted)
• 密度：
  1.024±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  43.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trichlorotris(tetrahydrofuran)chromium(III) 、 benzylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol) 在 正丁基锂 作用下， 以 正己烷 、 四氢呋喃 为溶剂， 反应 20.0h， 以95%的产率得到
  参考文献：
  名称：

  Chromium(iii) amine-bis(phenolate) complexes as catalysts for copolymerization of cyclohexene oxide and CO₂

  摘要：

  三/四牙胺基-双(酚酞)配体的铬络合物与氯化物、叠氮化物或DMAP亲核试剂的组合是CO₂与环己氧化物共聚合的有效催化剂，可以得到聚碳酸酯。

  DOI：

  10.1039/c3cy01002c
• 作为产物：
  描述：

  聚合甲醛 、 2,4-二叔丁基苯酚 、 苄胺 以 水 为溶剂， 反应 20.0h， 以47%的产率得到benzylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol)
  参考文献：
  名称：

  中性供体配体在rac-β-丁内酯的等价开环聚合中的作用

  摘要：

  富集异氰酸的3-羟基丁酸酯（P3HB）是一种可生物降解的材料，其性能与全同立构聚丙烯相似，但是经过50多年的催化剂设计广泛努力，仍缺乏有效的制备这种材料的途径。在这种贡献中，新型的氨基双酚镧镧（1-La）可以通过rac -β-丁内酯（rac -BBL）的立体有择开环聚合（ROP）进入等价富集的P3HB。用非配位的苄基取代基取代优先的支持配体的束缚供体基团，生成了一种催化剂，其反应性和选择性可以通过廉价的非手性中性供体配体（例如氧化膦，OPR 3）进行调节。在1香格里拉/ OPR 3（R = n-辛基，Ph）体系表现出高活性，并且是迄今为止rac -BBL ROP最具选择性的均相催化剂（0°C：P m = 0.8，TOF〜190 h -1）。结合反应性和光谱研究可深入了解活性催化剂的结构和ROP机理。两个1-的La（TPPO）2并用的绳系供体基团（一个结构上相关的催化剂2-Y ）下链端的立体控制操作;

  DOI：

  10.1039/d0sc03507f

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。
• CATALYST AND PROCESS FOR RING OPENING POLYMERIZATION
  申请人：Brown University

  公开号：US20210188878A1

  公开（公告）日：2021-06-24

  The present invention discloses new catalyst systems based on trivalent metal complexes of Formula I, which can facilitate the stereospecific ring-opening polymerization of (rac)-β-Butyrolactone (rac-BBL). Also provided is a process for the stereospecific synthesis of aliphatic polyesters using the catalysts of Formula I, including alcohols and polyols as chain-transfer agents to facilitate immortal ring-opening polymerization.

  本发明披露了基于三价金属配合物I式的新催化剂体系，可以促进(rac)-β-丁内酯(rac-BBL)的立体特异性开环聚合。同时提供了使用I式催化剂的立体特异性合成脂肪族聚酯的过程，包括使用醇和多元醇作为链转移剂以促进永久性开环聚合。
• <i>N</i>-Oxides amplify catalyst reactivity and isoselectivity in the ring-opening polymerization of <i>rac</i>-β-butyrolactone
  作者：Xiang Dong、Alexander M. Brown、Audra J. Woodside、Jerome R. Robinson

  DOI：10.1039/d1cc05127j

  日期：——

  N-Oxides can amplify the performance of a lanthanum aminobisphenolate catalyst in the ring-opening polymerization (ROP) of rac-β-butyrolactone (rac-BBL) to unprecedented levels (TOF/Pm; At RT: 1900 h−1/0.73, At −30 °C: 200 h−1/0.82). Experiments and computations establish donor electronics control catalyst activity, while donor sterics control catalyst deactivation.

  N-氧化物可以将氨基双酚镧催化剂在rac -β-丁内酯 ( rac -BBL)的开环聚合 (ROP) 中的性能提高到前所未有的水平 (TOF/ P m ; 在 RT: 1900 h -1 /0.73 ，在-30 °C：200 h -1 /0.82)。实验和计算确定供体电子控制催化剂活性，而供体空间控制催化剂失活。
• Synthesis of amino-phenolate manganese complexes and their catalytic activity in carbon dioxide activation and oxidation reactions
  作者：Ali I. Elkurtehi、Francesca M. Kerton

  DOI：10.1139/cjc-2020-0348

  日期：2021.2

  Two manganese(III) compounds were studied as catalysts for the reaction of carbon dioxide with propylene oxide, styrene oxide, and cyclohexene oxide, and formed cyclic carbonate products selectively under solvent free conditions in the presence of an ionic co-catalyst such as TBAB or PPNCl. Variable temperature kinetic studies allowed the activation energy for propylene carbonate formation to be determined (64 kJ mol⁻¹). The catalysts showed good stability in these reactions and overall turnover numbers (TON) of up to 6000 were observed. The complexes showed low activity for the aerobic oxidation of 4-methyoxybenzylalcohol to the corresponding aldehyde, achieving up to 40% conversion in 72 h. However, near quantitative conversion of 1,2-diphenyl-2-methoxyethanol to provide up to 90% yield of benzaldehyde could be achieved over the course of 5 days. Both complexes showed similar reactivity in the two catalytic processes, and this is likely due to the weakly coordinating nature of the pendant donor within the tetradentate ligand.
• The role of neutral donor ligands in the isoselective ring-opening polymerization of <i>rac</i>-β-butyrolactone
  作者：Xiang Dong、Jerome R. Robinson

  DOI：10.1039/d0sc03507f

  日期：——

  reactivity and selectivity can be tuned with inexpensive achiral neutral donor ligands (e.g. phosphine oxides, OPR3). The 1-La/OPR3 (R = n-octyl, Ph) systems display high activity and are the most isoselective homogeneous catalysts for the ROP of rac-BBL to date (0 °C: Pm = 0.8, TOF ∼190 h−1). Combined reactivity and spectroscopic studies provide insight into the active catalyst structure and ROP mechanism

  富集异氰酸的3-羟基丁酸酯（P3HB）是一种可生物降解的材料，其性能与全同立构聚丙烯相似，但是经过50多年的催化剂设计广泛努力，仍缺乏有效的制备这种材料的途径。在这种贡献中，新型的氨基双酚镧镧（1-La）可以通过rac -β-丁内酯（rac -BBL）的立体有择开环聚合（ROP）进入等价富集的P3HB。用非配位的苄基取代基取代优先的支持配体的束缚供体基团，生成了一种催化剂，其反应性和选择性可以通过廉价的非手性中性供体配体（例如氧化膦，OPR 3）进行调节。在1香格里拉/ OPR 3（R = n-辛基，Ph）体系表现出高活性，并且是迄今为止rac -BBL ROP最具选择性的均相催化剂（0°C：P m = 0.8，TOF〜190 h -1）。结合反应性和光谱研究可深入了解活性催化剂的结构和ROP机理。两个1-的La（TPPO）2并用的绳系供体基团（一个结构上相关的催化剂2-Y ）下链端的立体控制操作;