n-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol) | 267428-18-2

• 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-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol)
• 英文别名: N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)propylamine；MeCH2CH2N(2-HO-3,5-C6H2-t-Bu2)2；PrN(CH2-2-OH-3,5-C6H2(t-Bu)2)2；2,4-Ditert-butyl-6-[[(3,5-ditert-butyl-2-hydroxyphenyl)methyl-propylamino]methyl]phenol
• CAS: 267428-18-2
• 化学式: C₃₃H₅₃NO₂
• 分子量: 495.789
• InChiKey: RCWGQZBHKQEGRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  36
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  n-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol) 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：

  正丙胺 、 聚合甲醛 、 2,4-二叔丁基苯酚 以 水 为溶剂， 反应 12.0h， 以91%的产率得到n-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol)
  参考文献：
  名称：

  铁（iii）胺-双（酚盐）配合物对芳基格氏试剂的催化烷基化作用†

  摘要：

  正丙基氨基-N，N-双（2-亚甲基-4-叔丁基-6-甲基苯酚），H 2 L1，正丙基氨基-N，N-双（2-亚甲基-4,6-di）的反应-叔丁基苯酚），H 2 L2和苄氨基-N，N-双（2-亚甲基-4-叔丁基-6-甲基苯酚），H 2 L3（无水）氯化铁在碱的存在下产生产物[Fe L1（μ-Cl）] 2（1），[Fe L2（μ-Cl）] 2（2）和[Fe L3（μ-Cl）] 2（3） 。在固态下，这些络合物以氯桥联的二聚体形式存在，产生扭曲的三角双锥体铁（III）离子。然而，H 2 L1与FeBr 3的反应导致形成具有两个溴化物配体的四面体铁（III）配合物。胺-二（酚盐）配位体是在这种复杂的二齿并粘合到铁（III）离子通过酚盐O供体 中心胺供体被质子化，产生季铵化的铵碎片，并且铁（III）中心具有负的形式电荷。结果，该络合物是两性离子的，并配制成FeBr 2 L1H（4）。配合物1是一种空气

  DOI：

  10.1039/c0dt01239d

文献信息

• [EN] IRON BISPHENOLATE COMPLEXES AND METHODS OF USE AND SYNTHESIS THEREOF<br/>[FR] COMPLEXES BISPHÉNOLATES DE FER ET LEURS PROCÉDÉS D'UTILISATION ET DE SYNTHÈSE
  申请人：UNIV PRINCE EDWARD ISLAND

  公开号：WO2013053046A1

  公开（公告）日：2013-04-18

  The present application, relates to iron bisphenolate complexes and methods of use and synthesis thereof. The iron complexes are prepared from tridentate or tetradentate ligands of Formula I: wherein R1 and R2 are as defined herein. Also provided are methods and processes of using the iron bisphenolate complexes as catalysts in cross-coupling reactions and in controlled radical polymerizations.

  本申请涉及铁双酚酸酯配合物及其使用和合成方法。这些铁配合物是从三齿或四齿配体的化学式I制备而成的：其中R1和R2如本文所定义。还提供了使用铁双酚酸酯配合物作为催化剂进行交叉偶联反应和控制自由基聚合的方法和过程。
• Zwitterionic bis(phenolate)amine lanthanide complexes for the ring-opening polymerisation of cyclic esters
  作者：Hellen E. Dyer、Saskia Huijser、Andrew D. Schwarz、Chao Wang、Robbert Duchateau、Philip Mountford

  DOI：10.1039/b714583g

  日期：——

  The reaction of SmN(SiMe3)2}3 with the bis(phenol)amines H2O2NR (H2O2NR = RCH2CH2N(2-HO-3,5-C6H2tBu2)2; R = OMe, NMe2 or Me) gave exclusively zwitterions Sm(O2NR)(HO2NR). For R = OMe or NMe2 these were efficient catalysts for the ring-opening polymerisation of ε-caprolactone and D,L-lactide with a tendency to form cyclic esters; in contrast, no polymerisation was observed for R = Me.

  SmN(SiMe3)2}3与双酚胺H2O2NR（H2O2NR = RCH2CH2N(2-HO-3,5-C6H2tBu2）；R = OMe、NMe2或Me）的反应主要生成两性离子Sm(O2NR)(HO2NR)。对于R = OMe或NMe2，这些化合物是ε-己内酯和D,L-乳酸开环聚合的有效催化剂，并且有形成环状酯的倾向；而对于R = Me，则未观察到聚合反应。
• Ring-Opening Polymerization of <i>rac</i>-Lactide by Bis(phenolate)amine-Supported Samarium Borohydride Complexes: An Experimental and DFT Study
  作者：Hellen E. Dyer、Saskia Huijser、Nicolas Susperregui、Fanny Bonnet、Andrew D. Schwarz、Robbert Duchateau、Laurent Maron、Philip Mountford

  DOI：10.1021/om100513j

  日期：2010.8.23

  structures of 2, 5, 6, 7, 10, 13, and 14 were determined. The borohydrides 2−5 were very efficient initiators for the ROP of ε-CL, giving linear dihydroxytelechelic poly(ε-CL). Selected amide initiators were also assessed but gave poorer control, as judged by broad PDI (Mw/Mn) values and significant amounts of cyclic poly(ε-CL)s. Of the borohydrides, only 2−4 were active for the ROP of rac-LA, and activity

  报道了双（酚盐）胺负载的硼氢化mar和酰胺配合物的合成和开环聚合（ROP）能力，以及DFT研究。Na 2 O 2 N L（L = OMe，NMe 2，py或Pr）与Sm（BH 4）3（THF）3反应，得到硼氢化物络合物Sm（O 2 N L）（BH 4）（THF） （L = OMe（2），NMe 2（3）或py（4））或Sm（O 2 N Pr）（BH 4）（THF）2（5）。化合物4和5在真空中损失THF ，分别形成酚盐O桥联的二聚体1和6。H 2 O 2 N L与Sm N（SiHMe 2）2 } 3（THF）2反应形成单体Sm（O 2 N L）N（SiHMe 2）2 }（THF）（L = OMe（7） ，NMe 2（8）或py（9））具有四齿O 2 N L配体，但二聚体Sm2（μ-O 2 Ñ镨）2（O 2 Ñ镨）（THF）（10）具有三齿ö 2 Ñ镨。Sm N（SiMe 3）2 } 3与H
• 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 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