2-(benzyloxy)-1-(bromomethyl)-3,5-di-tert-butylbenzene | 925423-04-7

• 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: 2-(benzyloxy)-1-(bromomethyl)-3,5-di-tert-butylbenzene
• 英文别名: 1-(Bromomethyl)-3,5-ditert-butyl-2-phenylmethoxybenzene；1-(bromomethyl)-3,5-ditert-butyl-2-phenylmethoxybenzene
• CAS: 925423-04-7
• 化学式: C₂₂H₂₉BrO
• 分子量: 389.376
• InChiKey: HKZJQYOIGBIFGJ-UHFFFAOYSA-N

物化性质

• 熔点：
  97-99 °C
• 沸点：
  422.6±45.0 °C(Predicted)
• 密度：
  1.155±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(benzyloxy)-1-(bromomethyl)-3,5-di-tert-butylbenzene 在 palladium on activated charcoal 4 A molecular sieve 、 氢气 、 potassium carbonate 、 sodium iodide 作用下， 以 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 生成 (R)-N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-1-(2-hydroxy-3,5-di-tert-butylphenyl)ethylamine
  参考文献：
  名称：

  Enantiopure Pseudo-C₃-Symmetric Titanium Alkoxide with Propeller-Like Chirality

  摘要：

  An enantiopure amine tris(phenolate) ligand containing a single stereogenic center has been used to control the propeller-like chirality of a derived pseudo-C-3-symmetric titanium isopropoxide complex with excellent levels of diastereocontrol.

  DOI：

  10.1021/ol062655w
• 作为产物：
  描述：

  2-(benzyloxy)-3,5-di-tert-butylbenzaldehyde 在 sodium tetrahydroborate 、 三溴化磷 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 1.0h， 生成 2-(benzyloxy)-1-(bromomethyl)-3,5-di-tert-butylbenzene
  参考文献：
  名称：

  带有酚醚或酚盐侧臂的侧桥Cyclam过渡金属配合物

  摘要：

  摘要合成了带有酚醚或酚盐侧链的侧桥环芳烃过渡金属配合物（M = Ni（II），Cu（II）和Zn（II））。对于[NiL1] +和[CuL1] +，获得了苯氧基自由基的证据（分别在+0.74 V和+0.48 V处存在一个可逆峰），以及由于酚盐的质子化导致的OH氧化，在〜+ 1.24V。与相应的Cu（II）络合物相比，[Ni（L1）] 2+中的苯氧基自由基更难被0.26 V氧化。[Ni（L1）] 2+的UV-Vis数据表明，Ni（II）离子可能为4或6坐标，而[Cu（L1）] 2+中的Cu（II）离子为5坐标。[Ni（L2）] [（ClO4）2]的晶体结构中的Ni（II）离子具有扭曲的方平面几何形状，其中酚醚侧垂臂不参与配位球。

  DOI：

  10.1016/j.poly.2019.08.003

文献信息

• Synthesis, structure, and catalytic activity of palladium complexes with new chiral cyclohexane-1,2-based di-NHC-ligands
  作者：Gongwo Shigeng、Junkai Tang、Dao Zhang、Quanrui Wang、Zhenxia Chen、Linhong Weng

  DOI：10.1016/j.jorganchem.2011.12.008

  日期：2012.3

  A pair of novel palladium complexes [(1S,2S)-L]PdBr2} and [(1R,2R)-L]PdBr2} of chiral di-N-heterocyclic carbene ligands derived from chiral 1,2-cyclohexanediamine have been prepared in moderate to good yields and characterized by NMR, HRMS and X-ray single crystal diffraction studies. The obtained chiral NHC-Pd compound was able to catalyze the asymmetric Suzuki-Miyaura couplings of aryl bromides with arylboronic acids in good yields and moderate enantioselectivities (up to 61% ee). (C) 2012 Elsevier B. V. All rights reserved.
• Synthesis of Tröger's base derived ligands: PHZ-derivatized ligand with pendant donor arms
  作者：Carissa S. Hampton、Michael Harmata

  DOI：10.1016/j.tet.2016.07.056

  日期：2016.10

  A cyclic diamine ligand whose core structure was derived from Troger's base, and included additional pendant arms containing ancillary donor coordination sites was prepared and coordination with transition metals attempted. (C) 2016 Published by Elsevier Ltd.
• Brønsted Base-Induced Rearrangement and Nucleophilic Addition of O/N-Functionalized NHCs and Relative Group 4 Metal Complexes for Ethylene Polymerization Catalysis
  作者：Li Wan、Dao Zhang

  DOI：10.1021/acs.organomet.5b00862

  日期：2016.1.25

  The O/N-functionalized NHC precursors 1-[RNHC(O)CH2]-3-[2-OH-3,5-Bu-t(2)-(C6H2)CH2]-imidazolium bromide, [H-3(1a-f)]Br (a: R = 2,6-Pr-i(2)-(C6H3); b: R = 2,4,6-Me-3-(C6H2); c: R = 2,6-Me-2-(C6H3); d: R = 4-Me-(C6H4); e: R = 4-Cl-(C6H4.); f: R = Bu-t), have been synthesized and characterized. Reactions between the aryloxy/amido-NHC precursors [H-3(1a-e)]Br and Ag2O resulted in the NHC rearrangement to compounds [2-OH-3,5-(Bu-t)(2)-(C6H2)CH2] [R]NC(O)-CH2-(C3N2H3) (4a-e) in 68-89% yield. The preliminary study suggested that, after deprotonation, the o-quinone methide (o-QM) intermediate was in situ generated by the C-N cleavage and proton transfer of the resultant aryloxybenzyl NHCs, followed by the nucleophilic attack of o-QM to the nitrogen atom of the amido group. Treatment of salicylaldimine-functionalized NHC precursor 1-Pr-i-[2-HO-C6H2-3,5-Bu-t(2)-C(H)=N-CH2CH2]-imidazolium bromide, [H-2(2)]Br, with sodium hydride and group 4 metal sources MCl4(THF)(2) (M = Ti, Zr) step by step afforded rare zwitterionic complexes [M(13)Cl-4] (M = Ti, 10; Zr, 11) in 50-53% yield. The formation of phenolate-amine 13 was attributed to the nucleophilic addition of the formed NHC to the imine carbon after deprotonation. The corresponding products 4a and [Ti(13)Cl-4](2)(mu-O)} (12) from the controlled hydrolysis of 10 have been confirmed by X-ray single-crystal analysis. Two novel NHC precursors, H-2(5)}Br and [H-3(7)]Br, together with silver complex [Ag-2(5)(2)] (6) were conveniently derived. Several relative group 4 metal complexes, [MX2(k(2)-N,O-OC6H2-3,5-Bu-t(2)-C(H)=N-CH2CH2-Im)(2)] [Br](2) (M = Zr, X = Cl, 8; M = Hf, X = OSiMe3, 9) and [Ti(7)Cl-2] (14), have been prepared and tested for ethylene polymerization with MAO as cocatalyst. Complex 14 showed the highest catalytic activity of up to ca. 114 kg PE/(mol Ti.h.atm) to produce linear polymer.
• Enantiopure Pseudo-<i>C</i>₃-Symmetric Titanium Alkoxide with Propeller-Like Chirality
  作者：Philip Axe、Steven D. Bull、Matthew G. Davidson、Carly J. Gilfillan、Matthew D. Jones、Diane E. J. E. Robinson、Luke E. Turner、William L. Mitchell

  DOI：10.1021/ol062655w

  日期：2007.1.1

  An enantiopure amine tris(phenolate) ligand containing a single stereogenic center has been used to control the propeller-like chirality of a derived pseudo-C-3-symmetric titanium isopropoxide complex with excellent levels of diastereocontrol.
• Side-bridged cyclam transition metal complexes bearing a phenolic ether or a phenolate pendent arm
  作者：Ryan E. Mewis、Stephen J. Archibald

  DOI：10.1016/j.poly.2019.08.003

  日期：2019.10

  corresponding Cu(II) complex. UV–Vis data for [Ni(L1)]2+ suggests that the Ni(II) ion may be 4 or 6 coordinate whereas the Cu(II) ion in [Cu(L1)]2+ is five coordinate. The Ni(II) ion in the crystal structure of [Ni(L2)][(ClO4)2] possesses a distorted square-planar geometry in which the phenolic ether pendent arm is not involved in the coordination sphere. The cyclam ligand in this complex adopts a trans-II

  摘要合成了带有酚醚或酚盐侧链的侧桥环芳烃过渡金属配合物（M = Ni（II），Cu（II）和Zn（II））。对于[NiL1] +和[CuL1] +，获得了苯氧基自由基的证据（分别在+0.74 V和+0.48 V处存在一个可逆峰），以及由于酚盐的质子化导致的OH氧化，在〜+ 1.24V。与相应的Cu（II）络合物相比，[Ni（L1）] 2+中的苯氧基自由基更难被0.26 V氧化。[Ni（L1）] 2+的UV-Vis数据表明，Ni（II）离子可能为4或6坐标，而[Cu（L1）] 2+中的Cu（II）离子为5坐标。[Ni（L2）] [（ClO4）2]的晶体结构中的Ni（II）离子具有扭曲的方平面几何形状，其中酚醚侧垂臂不参与配位球。