(3,5-(t-Bu)2-2-(OH)C6H2CH=N(CH2)2(HCN(CH)2N(i-Pr))Br | 871114-82-8

• 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: (3,5-(t-Bu)2-2-(OH)C6H2CH=N(CH2)2(HCN(CH)2N(i-Pr))Br
• 英文别名: 3,5-(t)Bu2-2-(O)C6H2CH=NCH2CH2(CH(NCHCHN(i)Pr))*HBr
• CAS: 871114-82-8
• 化学式: Br*C₂₃H₃₆N₃O
• 分子量: 450.462
• InChiKey: WELUOOFYEXTRMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.78
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  41.4
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (3,5-(t-Bu)2-2-(OH)C6H2CH=N(CH2)2(HCN(CH)2N(i-Pr))Br 在 sodium hydride 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以75%的产率得到
  参考文献：
  名称：

  Brønsted碱诱导的O / N功能化NHC和相对4族金属络合物的重排和亲核加成反应，用于乙烯聚合反应

  摘要：

  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.

  DOI：

  10.1021/acs.organomet.5b00862
• 作为产物：
  描述：

  3,5-二叔丁基水杨醛 在 sodium hydroxide 作用下， 以 乙醚 、 乙醇 、 正己烷 、 水 为溶剂， 反应 96.0h， 生成 (3,5-(t-Bu)2-2-(OH)C6H2CH=N(CH2)2(HCN(CH)2N(i-Pr))Br
  参考文献：
  名称：

  掺有水杨醛二氨基官能化的N-杂环卡宾配体的钌（II）配合物，作为有效且通用的有机腈水合催化剂

  摘要：

  摘要我们描述了一种新的合成方法，该合成方法可合成含有水杨醛二氨基官能化的N-杂环卡宾（NHC）配体和膦共配体的钌（II）配合物。通过从相应的作为碳烯转移试剂的Ag-NHC配合物（2a-2d）进行重金属化，已以良好至极好的收率获得了配合物（3a-3d）。所有[Ru–NHC]配合物均已通过元素分析，光谱方法以及ESI质谱进行了表征。配体1a-1d通过在这些钌（II）配合物中转换为O，N，C螯合来显示其多功能性。所得络合物已被评估为在环境友好的介质中将腈选择性水合为伯酰胺以及相关酰胺键形成反应的潜在催化剂。该反应可耐受醚，羟基，硝基，溴，甲酰基，吡啶基，苄基和烷基官能团。该催化剂可稳定保持数周，并且可以回收并重复使用六次以上，而不会显着降低活性。

  DOI：

  10.1016/j.ica.2015.11.033

文献信息

• Aluminium Complexes of a Phenoxyimine Ligand with a Pendant Imidazolium Moiety: Synthesis, Characterisation and Evidence for Hydrogen Bonding in Solution
  作者：Stefano Milione、Fabia Grisi、Roberto Centore、Angela Tuzi

  DOI：10.1002/ejic.200800742

  日期：2008.12

  alkylaluminium complexes (phim)AlMe2 (1) and(phimid)AlR2+Br– [R = Me (2), R = iBu (3)] bearing the Schiff base ligands 3,5-tBu2-2-(OH)C6H2CH=NiPr (phim-H) and3,5-tBu2-2-(OH)C6H2CH=NCH2CH2[CH(NCHCHNiPr)]Br(phimid-H·Br) have been prepared and fully characterised. Complexes 1–3 each have a tetrahedral structure, with the aluminium atom surrounded by the oxygen and nitrogen atoms of the chelating ligand and two

  带有席夫碱配体 3,5-tBu2-2-(OH)C6H2CH 的新型烷基铝配合物 (phim)AlMe2 (1) 和 (phimid)AlR2+Br– [R = Me (2), R = iBu (3)] =NiPr (phim-H) 和 3,5-tBu2-2-(OH)C6H2CH=NCH2CH2[CH(NCHCHNiPr)]Br(phimid-H·Br) 已制备并充分表征。配合物 1-3 各有一个四面体结构，铝原子被螯合配体的氧和氮原子和两个烷基包围。phimid-H·Br 和配合物1 的结构已通过X 射线衍射研究确定。通过 1H NMR 光谱对 1-3 溶液结构的研究表明，配位的 phimid 配体参与与溴阴离子的氢键合。用 B(C6F5)3 处理 1 通过将 基团从 MeB( )3- 转移到最初形成的配位不饱和阳离子中间体，平稳地导致 (phim)Al( )Me (
• Synthesis of Cationic N-Heterocyclic Carbene Lanthanide Bromide and the Influence of N-Heterocyclic Carbene and Lanthanide Metals
  作者：Haisheng Yao、Jinguo Zhang、Yong Zhang、Hongmei Sun、Qi Shen

  DOI：10.1021/om100562q

  日期：2010.11.22

  The lithium salt of the novel amido-phenoxo-functionalized NHC L (L = [3,5-Bu-t(2)-2-(O)C6H2CH-(Bu-n)NH(CH2)(2)(CN(CH)(2)(NPr)-Pr-i})]), (LiL)(2) (1), was synthesized by the direct reaction of the salicylaldimino-functionalized imidazolium salt H2L'Br (L' = [3,5-Bu-t(2)-2-(O)C6H2CH=N(CH2)(2)(CN(CH)(2)(NPr)-Pr-i})]) with 2 equiv of (LiBu)-Bu-n and structurally characterized, Treatment of LnCl(3) with in situ formed 1 in a molar ratio of 1:1 at room temperature yielded the first cationic complexes [LnL(2)](+)[Br](-) (Ln = Y (2), Lu (3), Er (4)) in good yields. Treatment of Li(THF)Ln((NPr2)-Pr-i)(4) with 2 equiv of H2L'Br at -78 degrees C afforded the cationic complexes [L'(2)Ln(THF)(+)[Br](-) (Ln = Y (5) and Yb (6)) in desired yields. Each central metal in cations [LnL(2)](+) for 2-4 is coordinated by two L ligands, while the central metal in [L'(2)Ln(THF)](+) for 5 and 6 is ligated by two ligands and one THF molecule. The structures of NHC lanthanide bromides have been found to depend on both the size of the metal and the ligand.
• Synthesis of Salicylaldiminato-Functionalized N-Heterocyclic Carbene Complex of Nickel(II) and Its Catalytic Activity for Styrene Polymerization
  作者：Wanfei Li、Hongmei Sun、Muzi Chen、Zhiguo Wang、Dongmei Hu、Qi Shen、Yong Zhang

  DOI：10.1021/om050612y

  日期：2005.11.1

  novel potentially tridentate N-heterocyclic carbene (NHC) precursor, anionic sali-cylaldimine-functionalized imidazolium bromide, [3,5-Bu-t(2)-2-(HO)C6H2CH=NCH2CH2(CH-(NCHCHNPr)-Pr-i})Br] (HL center dot HBr, 2), was designed. The reaction of in situ-generated monoanionic tridentate salicylaldiminato-functionalized NHC LNa with Ni(PPh3)(2)Br-2 affords a novel monoligand Ni(H) bromide, [3,5-Bu-t(2)-2-(O)C6H2CH=NCH2CH2(C(NCHCHNPr)-Pr-i})]NiBr (LNiBr, 3), in good yield. Complex 3 can also be synthesized by the direct reaction of nickelocene (CP)(2)Ni or bis-indenyl Ni(II) complex (Ind)(2)Ni with 2 in high yield via the cyclopentadiene or indene elimination reaction, respectively. Complex 3 has been fully characterized including X-ray structural determination. Preliminary study indicated that 3 shows good catalytic activity for the polymerization of styrene in the presence of NaBPh4 at 80 degrees C.
• Lanthanide Carbene Halides through Protonolysis of Ln−N Bonds by Imidazolium Salts: Synthesis and Structure of Salicylaldiminato-Functionalized N-Heterocyclic Carbene Lanthanide Bromides
  作者：Jinguo Zhang、Haisheng Yao、Yong Zhang、Hongmei Sun、Qi Shen

  DOI：10.1021/om8001922

  日期：2008.6.9

  The three salicylaldiminato-functionalized N-heterocyclic carbene lanthanide bromides L(2)LnBr (Ln=Nd (2), Sm (3), Er (4); L=[3,5-(t)Bu(2)-2-(O)C(6)H(2)CH=NCH(2)CH(2)(CNCHCHN(i)Pr})]) with early to late lanthanide metals were conveniently synthesized in moderate yields by a protonolysis strategy via the direct reaction of LiLn(N(i)Pr(2))(4) with [H(2)L]Br (1). All complexes were characterized by X-ray crystal determinations.