(2-HO-3,5-(t-Bu)2C6H2NCH=CHN(Me)CH)Br | 1191914-70-1

• 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-HO-3,5-(t-Bu)2C6H2NCH=CHN(Me)CH)Br
• 英文别名: 3-(3,5-di-tert-butyl-2-hydroxyphenyl)-1-methyl-1H-imidazol-3-ium bromide
• CAS: 1191914-70-1
• 化学式: Br*C₁₈H₂₇N₂O
• 分子量: 367.329
• InChiKey: GGLGINRFXIGMRJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.61
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.04
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  dicarbonylcyclopentadienyliodoiron(II) 、 (2-HO-3,5-(t-Bu)2C6H2NCH=CHN(Me)CH)Br 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以30%的产率得到carbon monoxide;cyclopenta-1,3-diene;2,4-ditert-butyl-6-(3-methyl-2H-imidazol-1-ium-2-id-1-yl)phenolate;iron(2+)
  参考文献：
  名称：

  带有NHC配体的铁钢琴凳配合物，配有侧臂：合成，表征和催化转移氢化的筛选†

  摘要：

  已通过以下方法制备了两种含NHC配体的铁钢琴凳配合物，这些配合物配有含羟基的侧臂（脂肪族和芳香族）用强碱使咪唑鎓盐去质子化。当翼尖含有庞大的苯酚基团时，可以使用额外当量的碱来接近阴离子配体。X射线晶体学和DFT计算表明所得负电荷的明显离域，这显然使配合物稳定。使用FTIR光谱可测量的程度强的给体配体会在一定程度上影响铁中心的电子环境。使用2-丙醇作为溶剂和氢供体，筛选该复合物用于苯甲醛，苯乙酮和二苯甲酮的催化转移氢化。可见光下的分子配合物对羰基的还原没有反应性。试图提高原位催化剂的周转率 在两种情况下，使用紫外线的条件都会导致不希望的苯乙酮光诱导的松果醇化，并且含芳族的NHC配合物分解为铁镜。

  DOI：

  10.1039/c6ra20764b
• 作为产物：
  描述：

  2,4,6-三叔丁基苯酚 在 磷酸三甲酯 、 溴 作用下， 以 乙二醇 为溶剂， 生成 (2-HO-3,5-(t-Bu)2C6H2NCH=CHN(Me)CH)Br
  参考文献：
  名称：

  An attractive route to transamidation catalysis: Facile synthesis of new o-aryloxide-N-heterocyclic carbene ruthenium(II) complexes containing trans triphenylphosphine donors

  摘要：

  Well-defined robust ruthenium(II) complexes 3a-d bearing o-aryloxide-N-heterocyclic carbene ligands with different wingtip substituents (3a (R= Me), 3b (R= Ph), 3c (R= Pr-i) and 3d (R= Mes)) in the imidazole ring were synthesized in good yields by the reaction of imidazolium proligands with metal precursor [RuHCl(CO)(PPh3)(3)] by transmetallation from the corresponding silver carbene complexes. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The molecular structure of the complex 3a was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted octahedral geometry. In order to explore the catalytic potential of the synthesized complexes, all the four [Ru-NHC] complexes [3a-d] were tested as catalysts for transamidation of carboxamides with amines. Notably, the complex 3a was found to be very efficient and versatile catalyst toward transamidation of a wide range of amides with amines. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.03.015
• 作为试剂：
  描述：

  苯乙酮 在 dicarbonylcyclopentadienyliodoiron(II) 、 (2-HO-3,5-(t-Bu)2C6H2NCH=CHN(Me)CH)Br 、 potassium hydroxide 作用下， 以 异丙醇 为溶剂， 生成 苏合香醇
  参考文献：
  名称：

  带有NHC配体的铁钢琴凳配合物，配有侧臂：合成，表征和催化转移氢化的筛选†

  摘要：

  已通过以下方法制备了两种含NHC配体的铁钢琴凳配合物，这些配合物配有含羟基的侧臂（脂肪族和芳香族）用强碱使咪唑鎓盐去质子化。当翼尖含有庞大的苯酚基团时，可以使用额外当量的碱来接近阴离子配体。X射线晶体学和DFT计算表明所得负电荷的明显离域，这显然使配合物稳定。使用FTIR光谱可测量的程度强的给体配体会在一定程度上影响铁中心的电子环境。使用2-丙醇作为溶剂和氢供体，筛选该复合物用于苯甲醛，苯乙酮和二苯甲酮的催化转移氢化。可见光下的分子配合物对羰基的还原没有反应性。试图提高原位催化剂的周转率 在两种情况下，使用紫外线的条件都会导致不希望的苯乙酮光诱导的松果醇化，并且含芳族的NHC配合物分解为铁镜。

  DOI：

  10.1039/c6ra20764b

文献信息

• Selective and catalytic carbon dioxide and heteroallene activation mediated by cerium N-heterocyclic carbene complexes
  作者：Polly L. Arnold、Ryan W. F. Kerr、Catherine Weetman、Scott R. Docherty、Julia Rieb、Faye L. Cruickshank、Kai Wang、Christian Jandl、Max W. McMullon、Alexander Pöthig、Fritz E. Kühn、Andrew D. Smith

  DOI：10.1039/c8sc03312a

  日期：——

  )]2 (R = Me, iPr) are reported, along with a hexanuclear N-heterocyclic dicarbene [Li2Ce3(OArCMe–H)3(NiPr2)5(THF)2]2 by-product. The analogous para-aryloxide–NHC proligand (p-LMes = 4-O-2,6-tBu2-C6H2(1-CN(CH)2NMes}))) has been made for comparison, but the rare earth tris-ligand complexes Ln(p-LMes)3(THF)2 (Ln = Y, Ce) are too reactive for straightforward Lewis pair separated chemistry to be usefully

  据报道，由双齿正邻芳基氧化物-NHC配体支持的一系列Ln（L R）3形式的稀土配合物（L R = 2-O-3,5- t Bu 2 -C 6 H 2（1-C N（CH）2 N（R）}））；R = i Pr，t Bu，Mes; Ln = Ce，Sm，Eu）。铈络合物干净，定量地仅将二氧化碳插入所有三个铈卡宾键中，形成Ce（L R ·CO 2）3。该插入仅对于异丁基取代的复合物Ce（L Mes）3是可逆的。Ce（L R）3插入一系列与CO 2等电子的杂烯的能力的分析揭示了选择性对溶剂和配体尺寸的依赖性。这很重要，因为只有能够逆转插入CO 2的络合物才是催化转化CO 2的有效催化剂。初步研究表明，只有Ce（L Mes ·CO 2）3在1 atm大气压的CO 2压力下催化由环氧丙烷形成碳酸亚丙酯。可以使用LiCe（N i Pr 2）4从反应中分离出单配体络合物作为起始原料；报道了溴化锂加合物[Ce（L
• Synthesis, Structures, and Norbornene Polymerization Behavior of Bis(aryloxide-N-heterocyclic carbene) Palladium Complexes
  作者：Yong Kong、Hongping Ren、Shansheng Xu、Haibin Song、Binyuan Liu、Baiquan Wang

  DOI：10.1021/om900625r

  日期：2009.10.26

  different N-substituted imidazoles. Treatment of the pro-ligands with Pd(OAc)2 afforded the corresponding bis(aryloxide-NHC) palladium complexes (NHC = N-heterocyclic carbene). The N-substituents at the NHCs were found to have significant effects on the structures of the bis(aryloxide-NHC) palladium complexes. Trans isomers were obtained when R = Me and iPr, while cis isomers were obtained for R = Ph

  通过4-溴-2,4,6-三叔丁基-2,5-环己二烯-1-酮（1）与不同氮原子的反应合成了一系列邻羟基芳基咪唑啉鎓原配体3a - 3e。取代的咪唑。用Pd（OAc）2处理前配体得到相应的双（芳氧基-NHC）钯配合物（NHC = N-杂环卡宾）。发现NHCs上的N-取代基对双（芳基氧化物-NHC）钯配合物的结构有重大影响。反式得到的异构体时，R =我和我PR，而顺式为R = P h和的MES得到异构体（MES =异亚丙基丙酮）。但是，对于R =于t Bu，获得具有正常和异常NHC配体的顺式异构体。所有这些配合物都通过1 H和13 C NMR和HRMS光谱进行了表征。所述前配体的分子结构图3b和络合物4 - 8通过单晶X射线衍射分析来确定。用甲基铝氧烷（MAO）作为助催化剂，这些双（芳氧基-NHC）钯络合物在降冰片烯的加成聚合反应中，在高达10 7 g的PNB（Pd摩尔） -1 h -1时显示出出色的催化活性。
• Synthesis, Structures, and Norbornene Polymerization Behavior of <i>o</i>-Aryloxide-Substituted NHC-Ligated σ, π-Cycloalkenyl Palladium Complexes
  作者：Liang Dang、Haibin Song、Baiquan Wang

  DOI：10.1021/om500839w

  日期：2014.12.8

  Treatment of the pro-ligand (2-OH-3,5-(Bu2C6H2)-Bu-t)(Mes)(C3H3N2)Br+ (2a) with di[mu-chloro-2 eta(2),5 eta(1)-(6-methoxy-endo-bicyclo[2.2.1]-hept-2-enyl)palladium(II)] (1a) and K(2)CO3 in dioxane, or reaction of the pro-ligand 2a subsequently with (BuLi)-Bu-n and 1a in THF afforded the o-aryloxide-substituted NHC-ligated s, p-cycloalkenyl palladium complex 3. Similarly, treatment of the pro-ligands (2-OH-3,5-tBu(2)C(6)H(2))(R)(C3H3N2)Br+ [R = Mes (2a), Me (2b), iPr (2c), Ph (2d)] with bis[mu-chloro-1 eta(2),5 eta(1)-(6-ethoxy-exo-5,6-dihydrodicyclopentadienyl)palladium(II)] (1b) and K2CO3 in dioxane afforded the desired products 49. All these complexes were fully characterized by H-1 and C-13 NMR, high-resolution mass spectrometry (HRMS), and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures of 36. With methylaluminoxane (MAO) as cocatalyst, these complexes showed excellent catalytic activities up to 10(7) g of PNB (mol of Pd) (-1) h(-1) in the addition polymerization of norbornene.
• Synthesis, Structures, and Norbornene ROMP Behavior of <i>o</i>-Aryloxide-N-Heterocyclic Carbene <i>p</i>-Cymene Ruthenium Complexes
  作者：Yong Kong、Shansheng Xu、Haibin Song、Baiquan Wang

  DOI：10.1021/om300474n

  日期：2012.8.13

  Treatment of the o-hydroxyaryl imidazolium proligands (2-OH-3,5-(Bu2C6H2)-Bu-t)(R)(C3H3N2)Br-+(-) (R = Pr-i (Ia), Bu-t (1b), Ph (1c), Mes (1d)) with 3 equiv of Ag2O afforded the corresponding silver complexes 2a-d. The subsequent metal-exchange reactions with [(p-cymene)-RuCl2](2) at room temperature yielded the desired o-aryloxide-N-heterocyclic carbene p-cymene ruthenium complexes 3a-d in nearly quantitative yields. All the complexes were characterized by H-1 and C-13 NMR, high-resolution mass spectrometry (HRMS), and elemental analysis. The molecular structure of complex 3b was determined by single-crystal X-ray diffraction analysis. The ring-opening metathesis polymerization (ROMP) of norbornene (NBE) with 3a-d was studied. Among them, complex 3d showed high activity and efficiency toward ROMP of NBE at 85 degrees C without the need for any cocatalyst, and polymers with very high molecular weight (>10(6)) and narrow molecular weight distributions were obtained. This complex can also catalyze the alternating copolymerization of NBE and cyclooctene (COE).
• Synthesis, Structures, and Norbornene Polymerization Behavior of Aryloxide-N-Heterocyclic Carbene Ligated Palladacycles
  作者：Yong Kong、Lifang Wen、Haibin Song、Shansheng Xu、Min Yang、Binyuan Liu、Baiquan Wang

  DOI：10.1021/om100994s

  日期：2011.1.10

  Treatment of the o-hydroxyaryl imidazolinium pro-ligands (2-OH-3,5-(Bu2C6H2)-Bu-t)(R)(C3H3N2)Br-+(-) [R = Me (3a), Pr-i (3b), Bu-t (3c), Ph (3d), Mes (3e)] with the palladacycle [Pd(dmba)(mu-Cl)](2) (dmba = Me2NCH2C6H5) (2) afforded the corresponding aryloxide-NHC (NHC = N-heterocyclic carbene)-ligated palladacycles (2-O-3,5-(Bu2C6H2)-Bu-t)(R)(NHC)Pd(dmba) [R = Me (4), Pr-t (5), Ph (6), Mes (7), Bu-t (8)]. Notably, without isolating 2, complexes 4-8 could also be obtained by one-pot, three-component, sequential reaction of N,N-dimethylbenzylamine, PdCl2, and the pro-ligands in refluxing acetonitrile in the presence of K2CO3. When the N-functional group on the NHCs is tert-butyl, the NHC in 8 adopts an abnormal binding (C4-bonding). All these complexes were fully characterized by H-1 and C-13 NMR, high-resolution mass spectrometry (HRMS), and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures of 4-8 and the abnormal binding of NHC in 8. With methylaluminoxane (MAO) as cocatalyst these palladacycles showed excellent catalytic activities up to 10(7) g of PNB (mol of Pd)(-1) h(-1) in the addition polymerization of norbornene.