2,4-di-tert-butyl-6-((phenylimino)methyl)phenol | 97746-37-7

• 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: 2,4-di-tert-butyl-6-((phenylimino)methyl)phenol
• 英文别名: 2,4-Di-tert-butyl-6-phenyliminomethylphenol；2,4-ditert-butyl-6-(phenyliminomethyl)phenol
• CAS: 97746-37-7
• 化学式: C₂₁H₂₇NO
• 分子量: 309.451
• InChiKey: YNRMRJMVFVZTMD-UHFFFAOYSA-N

物化性质

• 熔点：
  115 °C(Solv: chloroform (67-66-3); methanol (67-56-1))
• 沸点：
  408.7±45.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,4-di-tert-butyl-6-((phenylimino)methyl)phenol 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以99%的产率得到Lithium;2,4-ditert-butyl-6-(phenyliminomethyl)phenolate
  参考文献：
  名称：

  Metal and Ligand-Substituent Effects in the Immortal Polymerization ofrac-Lactide with Li, Na, and K Phenoxo-imine Complexes

  摘要：

  A series of lithium, sodium, and potassium complexes with phenoxo-imine ligands M[(O-2-(RN=CH)-C6H4] [R = C6H5; 2-(BuC6H5)-Bu-t; 2,6-(Pr2C6H3)-Pr-i] and [O-2-(RN=CH)-4,6-(Bu2C6H4)-Bu-t] [R = C6H5; 2-(BuC6H5)-Bu-t; 2,6-(Pr2C6H3)-Pr-i] 1-3(a-f) have been synthesized. The molecular structures in the solid state of some of these complexes have been determined by X-ray diffraction. These compounds show different nuclearities and geometries around the metal center depending on the nature and the pocket of the ligand substituents. Of particular interest is the structure of compound 3e, being the first example of a potassium cubane complex obtained with this kind of ligand. The structural behavior in solution has also been studied by diffusion-ordered NMR spectroscopy (DOSY), showing a direct correlation between aggregation behavior and polymerization activity. Compounds 1-3(a-f) are extremely active catalysts in the ring-opening polymerization (ROP) of rac-lactide, achieving conversions of 100% in less than 1 min and heterorich-PLA that is modified by the metal atom and the ligand substituents. BnOH was used as co-initiator, and the presence of large amounts of the alcohol produces the immortal polymerization of rac-lactide in a more controlled process. Stoichiometric reactions involving the catalysts, BnOH, and lactide demonstrated an activated monomer mechanism for the polymerization of rac-lactide.

  DOI：

  10.1021/om501000b
• 作为产物：
  描述：

  2,4-二叔丁基苯酚 在 三乙胺 、 magnesium chloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 28.0h， 生成 2,4-di-tert-butyl-6-((phenylimino)methyl)phenol
  参考文献：
  名称：

  N,O-供体希夫碱配体的 Pd(II) 配合物催化的 Suzuki-Miyaura 交叉偶联反应

  摘要：

  评估了由二齿 N,O-供体配体合成的 Pd(II) 配合物对卤代芳烃（碘/溴/氯）与给电子/吸电子基团之间Suzuki-Miyaura CC 偶联反应的催化活性含有苯基硼酸。N,O-供体配体由水杨醛、3,5-二叔丁基水杨醛、3-叔丁基水杨醛、5-叔丁基水杨醛与苯胺和苯胺衍生物合成。通过单晶XRD对配合物5c、5f、5h、5j和5t的单晶进行衍射，这些Pd(II)配合物的晶体结构表示反式几何学。探索了铃木-宫浦反应中具有电子和空间效应的配体的不同 Pd(II) 配合物。此外，还研究了苯硼酸和芳基卤化物催化偶联的反应参数，例如底物与碱(K 2 CO 3 )的比例、温度、溶剂、催化剂负载量、空间和电子效应。Pd(II)催化剂5a在广泛的给电子/吸电子芳基碘化物和芳基溴化物中具有高活性。K 2 CO 3存在下的催化剂5a ( 0.05 mol%)120 °C 的 DMF 碱对多种含有给电子/吸电子基团的苯基硼酸表现出优异的活性，2-4

  DOI：

  10.1016/j.poly.2023.116655

文献信息

• Monocyclopentadienyl Phenoxido–Amino and Phenoxido–Amido Titanium Complexes: Synthesis, Characterisation, and Reactivity of Asymmetric Metal Centre Derivatives
  作者：Giuseppe Alesso、Martial Sanz、Marta E. G. Mosquera、Tomás Cuenca

  DOI：10.1002/ejic.200800553

  日期：2008.10

  /ethyl ether solution. The reaction of TiCpCl 3 with 2a in the presence of 2.5 equiv. of NEt 3 in a polar solvent (thf, CH 2 Cl 2 or toluene) at room temperature affords TiCp[Ph(H)NCH2(3,5-tBu 2 C 6 H 2 -2-O)]Cl (6a) as a mixture of two stereoisomers. All the reported compounds were characterised by the usual analytical and spectroscopic methods and the molecular structures of 2a, 2d, 2e and 3d were

  酚亚胺衍生物的还原 R'N=CH(3,5-R 2 C 6 H 2 -2-OH) (R = tBu; R' = C 6 H 5 la, p-MeC 6 H 4 1b, Cy 1c, tBu 1d, 2,6-Me 2 C 6 H 3 1e；R = H；R' = p-MeC 6 H 4 1f；Cy = 环己基）与 MBH 4 (M = Li, Na) 或 AlLiH 4 in乙醚或 thf 在室温下得到苯酚-胺化合物 R'NHCH2(3,5-R2C 6 H 2 -2-OH) 2a-c 和 2e,f。NR-[2,4-二-叔丁基]苯并-1-oxa-3-azine物质（R = tBu 2dl, 2,6-Me 2 C 6 H 3 2el）通过2的曼尼希反应获得， 4-二叔丁基苯酚与 RNH 2 在回流甲醇中。中间体2dl在室温下在乙醇中转化为N-叔丁基[2-羟基-3,5-二-叔丁基]苄胺(2d)，而2e
• Ruthenium( <scp>II</scp> ) Complexes Bearing Schiff Base Ligands for Efficient Acceptorless Dehydrogenation of Secondary Alcohols ^†
  作者：Zhiqiang Hao、Kang Liu、Qi Feng、Qing Dong、Dongzhu Ma、Zhangang Han、Guo‐Liang Lu、Jin Lin

  DOI：10.1002/cjoc.202000363

  日期：2021.1

  Four ruthenium(II) complexes 1—4 [RN=CH‐(2,4‐(tBu)2C6H2O)]RuH(PPh3)2(CO) (R = C6H5, 1; R = 4‐MeC6H4, 2; R = 4‐ClC6H4, 3; R = 4‐BrC6H4, 4) bearing Schiff base ligands were prepared by treating RuHClCO(PPh3)3 with RN=CH‐(2,4‐(tBu)2C6H2OH (L1—L4) in the presence of triethylamine. Their structures were fully characterized by elemental analysis, IR, NMR spectroscopy and X‐ray crystallography. These Ru(II)

  四个钌（II）配合物1-4 [RN = CH-（2,4-（t Bu）2 C 6 H 2 O）] RuH（PPh 3）2（CO）（R = C 6 H 5，1 ; R = 4-MEC 6 ħ 4，2; R = 4-CLC 6 ħ 4，3; R = 4- BRC 6 ħ 4，4）的轴承的席夫碱配体通过处理制备RuHClCO（PPH 3）3与RN = CH‐（2,4‐（t Bu）2碳6 H 2在三乙胺存在下的OH（L1-L4）。它们的结构已通过元素分析，IR，NMR光谱和X射线晶体学充分表征。这些Ru（II）配合物在仲醇的无受体脱氢反应中显示出高催化性能和良好的官能团相容性，提供相应的酮，产率为82％-94％。
• Highly efficient oxidation of alcohols catalyzed by Ru(II) carbonyl complexes bearing salicylaldiminato ligands
  作者：Kang Liu、Junhua Zhang、Shuaicong Huo、Qing Dong、Zhiqiang Hao、Zhangang Han、Guo-Liang Lu、Jin Lin

  DOI：10.1016/j.ica.2019.119224

  日期：2020.1

  Reaction of Ru3(CO)12 with 2.0 equiv of RN = CH(3,5-tBu2C6H2OH) (R = C6H5, L1; R = 4-MeC6H4, L2; R = 4-OMeC6H4, L3; R = 4-ClC6H4, L4; R = 4-BrC6H4, L5; R = 4-CF3C6H4, L6) in refluxing xylene afforded the corresponding bis-chelate Ru(II) complexes 1a–1f [RN = CH(3,5-tBu2C6H2O)]2Ru(CO)2 and one of the imine bonds reduced complexes [RN = CH(3,5-tBu2C6H2O)]-[RNH-CH2(3,5-tBu2C6H2O)]}Ru(CO)2 2a–2f. All the

  Ru3（CO）12与2.0当量的RN = CH（3,5-tBu2C6H2OH）（R = C6H5，L1; R = 4-MeC6H4，L2; R = 4-OMeC6H4，L3; R = 4-ClC6H4 ，L4； R = 4-BrC6H4，L5; R = 4-CF3C6H4，L6）在回流的二甲苯中得到相应的双螯合物Ru（II）配合物1a-1f [RN = CH（3,5-tBu2C6H2O）] 2Ru（ CO）2和亚胺键之一还原了络合物[RN = CH（3,5-tBu2C6H2O）]-[RNH-CH2（3,5-tBu2C6H2O）]} Ru（CO）2 2a-2f。所有钌配合物均已通过NMR，IR和元素分析充分表征。此外，配合物1a-1f，2b，2d和2f的结构通过单晶X射线衍射进一步证实。当用N-甲基吗啉-N-氧化物（NMO）活化时，这些Ru络合物显示出对1°和2°醇氧化的高催化活性。在大多
• A Reusable Co Catalyst for the Selective Hydrogenation of Functionalized Nitroarenes and the Direct Synthesis of Imines and Benzimidazoles from Nitroarenes and Aldehydes
  作者：Tobias Schwob、Rhett Kempe

  DOI：10.1002/anie.201608321

  日期：2016.11.21

  presence of highly hydrogenation‐sensitive functional groups, as well as the direct synthesis of imines from nitroarenes and aldehydes or ketones in the presence of such substituents. Furthermore, we introduce the first base‐metal‐mediated direct synthesis of benzimidazoles from nitroarenes and aldehydes. Functional groups that are easy to hydrogenate are again well tolerated.

  在已优先由稀有贵金属介导的反应（例如氢化）中使用大量可利用的过渡金属是催化的理想目标，也是元素守恒的诱人策略。用这种廉价的金属催化剂观察新颖的选择性图特别有吸引力。在本文中，我们报道了一种新颖，坚固且可重复使用的钴催化剂，该催化剂可在高度氢化敏感的官能团存在下对硝基芳烃进行选择性氢化，以及在此类芳烃存在下由硝基芳烃和醛或酮直接合成亚胺取代基。此外，我们介绍了第一种由贱金属介导的由硝基芳烃和醛直接合成苯并咪唑的方法。易于氢化的官能团再次被很好地耐受。
• The use of Cu and Zn salicylaldimine complexes as catalyst precursors in ring opening polymerization of lactides: ligand effects on polymer characteristics
  作者：Suraj Bhunora、Jane Mugo、Archana Bhaw-Luximon、Selwyn Mapolie、Juanita Van Wyk、James Darkwa、Ebbe Nordlander

  DOI：10.1002/aoc.1728

  日期：2011.2

  copper (II) and zinc (II) complexes based on N,O‐bidentate salicylaldimine Schiff base ligands has been synthesized and characterized using various spectroscopic techniques. These complexes were then evaluated as initiators in ring‐opening polymerization of lactides at both 70 °C and 110 °C. The effect of structural changes in the complexes on the ability of these compounds to initiate lactide polymerization

  基于各种N，O-二齿水杨基亚胺席夫碱配体的一系列单体四配位铜（II）和锌（II）配合物已被合成并使用各种光谱技术进行了表征。然后在70°C和110°C下，评估这些络合物作为丙交酯开环聚合反应的引发剂。配合物的结构变化对这些化合物引发丙交酯聚合能力的影响以及对所得聚合物的化学和物理特性的影响表明，金属配合物的配位几何结构MSchiff碱配体上的O键长度和取代基均在催化剂活性中起作用。在铜配合物中，电子因素占主导地位，而在锌引发剂中，空间因素占主导地位。Zn和Cu络合物均显示活性环开环聚合的特征。版权所有©2010 John Wiley＆Sons，Ltd.