2,6-bis(1-methylethyl)-N-[(6-methyl-2-pyridinyl)methylene]phenylamine | 215459-01-1

• 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: 2,6-bis(1-methylethyl)-N-[(6-methyl-2-pyridinyl)methylene]phenylamine
• 英文别名: pyridine-5-CH3-2-C(H)=N(2,6-(i-C3H7)2C6H3))；N-[2,6-di(propan-2-yl)phenyl]-1-(6-methylpyridin-2-yl)methanimine
• CAS: 215459-01-1
• 化学式: C₁₉H₂₄N₂
• 分子量: 280.413
• InChiKey: CDDCUICKMDRSDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  25.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-bis(1-methylethyl)-N-[(6-methyl-2-pyridinyl)methylene]phenylamine 在 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 以98%的产率得到N-(2,6-diisopropylphenyl)-N-(pyridin-2-ylmethyl)amine
  参考文献：
  名称：

  1,3-丁二烯的高度化学选择性和立体选择性顺式1,4-聚合的新型（苯甲基甲基）吡啶钛（IV）和锆（IV）催化剂前体

  摘要：

  已经合成了带有苯胺基甲基吡啶配体的第4组金属配合物，并通过核磁共振（NMR）光谱，元素分析和单晶X射线衍射分析对其进行了表征。在使用Al i Bu 2 H和甲基铝氧烷（MAO）活化后，所有配合物均在1,3-丁二烯和α-烯烃聚合反应中进行了测试。锆配合物相对于钛同源物显示出更高的活性。在所有情况下，乙烯的聚合导致高分子量线性聚乙烯的生产。丙烯聚合测试提供了基本上无规的聚丙烯。1,3-丁二烯聚合反应生成顺式-1,4聚丁二烯，在锆配合物的情况下，聚合物的含量为提供了更高的顺式-1,4个单位（99.9％）。催化剂的活性和立体选择性与配合物的空间特征有关。

  DOI：

  10.1021/ma1028455
• 作为产物：
  描述：

  6-甲基-2-吡啶基甲醇 在 manganese(IV) oxide 、 硫酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 8.0h， 生成 2,6-bis(1-methylethyl)-N-[(6-methyl-2-pyridinyl)methylene]phenylamine
  参考文献：
  名称：

  Synthesis, structures of (aminopyridine)nickel complexes and their use for catalytic ethylene polymerization

  摘要：

  一系列α-氨基吡啶类化合物(2,6-C6H3N)(R1)(CHR2NR3R4)(R1 = R2 = H, R3 = H, R4 = iPr (L1a), R4 = tBu (L1b), R4 = Ph (L1c), R4 = 2,6-Me2C6H3 (L1d), R4 = 2,6-iPr2C6H3 (L1e), R1 = R2 = H, R3 = R4 = Et (L1f), R1 = H, R2 = Me, R3 = H, R4 = iPr (L2a), R4 = Ph (L2c), R4 = 2,6-Me2C6H3 (L2d), R4 = 2,6-iPr2C6H3 (L2e), R1 = Me, R2 = H, R3 = H, R4 = 2,6-iPr2C6H3 (L3e))和β-氨基吡啶类化合物(2-C6H4N)(CH2CH2NR1R2)(R1 = H, R2 = iPr (4a), R2 = tBu (L4b), R1 = R2 = Et (L4f))已被合成。通过配体取代反应从(DME)NiBr2合成相应的卤化镍配合物1a–4f,并由X射线晶体学表征其分子结构。通过X射线结晶学确定了四种配位模式,包括单核四配位物种与一个配体、单核五配位物种与两个配体、双核五配位物种与两个配体以及六配位的聚合框架。使用甲基铝氧烷(MAO)作为活化剂,镍配合物可以在中等压力和室温下催化乙烯聚合。活性达到105 g PE mol−1 Ni h。具有高度支化和高度结晶性的PE产品,Mn ∼ 103,PDI < 2。

  DOI：

  10.1039/c2dt30151b
• 作为试剂：
  描述：

  二甲基-2.2-二(丙-2-炔基)丙二酸二乙酯 在 trimethylsilylmethyllithium 、 频那醇硼烷 、 cobalt(II) chloride 、 2,6-bis(1-methylethyl)-N-[(6-methyl-2-pyridinyl)methylene]phenylamine 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以24%的产率得到dimethyl 5-(2,2-bis(methoxycarbonyl)pent-4-yn-1-yl)-1,3-dihydro-2H-indene-2,2-dicarboxylate
  参考文献：
  名称：

  1,4,6-二炔与品那可烷硼烷的钴催化环化/加氢硼化。

  摘要：

  在本文中，我们报告了一种使用频哪醇硼烷使用从Co（II）-菲咯啉配合物，氟化四丁基铵和频萘酚硼烷原位生成的钴催化剂进行1,6-二炔与环己硼烷的环化/加氢硼化的方案。该方案具有良好的官能团耐受性，广泛的底物范围和出色的立体选择性，可从易于获得的原料合成有用的环状1,3-二烯基硼化合物。如对照实验所示，所提出的机理涉及低价钴促进的环金属化和随后的硼氢化。我们的发现表明，将硼氢化与CC键形成相结合是合成结构多样的有机硼烷的有效方法。

  DOI：

  10.1021/acs.orglett.9b02873

文献信息

• Bis-alkoxycarbonylation of styrene by pyridinimine palladium catalysts
  作者：Claudio Bianchini、Hon Man Lee、Giuseppe Mantovani、Andrea Meli、Werner Oberhauser

  DOI：10.1039/b108804c

  日期：2002.4.2

  Pyridinimine-modified Pd(II) complexes of general formulae (N-N′)Pd(Y)2 catalyze the methoxycarbonylation of styrene to give dimethyl phenylsuccinate as the largely major product [N-N′ = py-2-C(R)N(2,6-R′C6H3), R = H, Me; R′ = Me, i-Pr; 6-Mepy-2-C(H)N[2,6-(i-Pr)2C6H3]; py-2-C(H)N(C6H5); Y = acetate, trifluoroacetate]. The influence of various catalytic parameters on the overall conversion of styrene to carbonylated products and on the product selectivity has been studied by systematically varying the type of palladium initiator, the concentrations of organic oxidant (1,4-benzoquinone) and protic acid (p-toluenesulfonic acid), and the CO pressure. By an appropriate choice of the structure of the pyridinimine ligand and of the reaction parameters, turn-over numbers as high as 96 and selectivities in dimethyl phenylsuccinate as high as 98% were obtained. In particular, the overall conversion of styrene is controlled by the steric properties of the alkyl substituents on the imine aryl group, while the nature of the substituent (H or Me) on the imine carbon influences the selectivity. The addition of 2 equivalents of TsOH to the catalytic mixtures generally increased the styrene conversion but lowered the selectivity in dimethyl phenylsuccinate due to greater production of methyl 3,6-diphenyl-4-oxohexanoate. Further additions of TsOH (up to 6 equivalents) resulted in better selectivities and lower conversions for all precursors.

  一般公式为 (N-N′)Pd(Y)2 的吡啶亚胺修饰的 Pd(II)配合物催化苯乙烯甲氧羰基化生成二甲基苯基琥珀酸酯作为主要产物 [N-N′= 吡啶-2-C(R)N(2,6-R′C6H3), R= H, Me; R′= Me, i-Pr; 6-Mepy-2-C(H)N[2,6-(i-Pr)2C6H3]; 吡啶-2-C(H)N(C6H5); Y= 乙酸酯, 三氟乙酸酯]。通过系统改变钯引发剂类型、有机氧化剂(1,4-苯醌)和质子酸(对甲苯磺酸)的浓度以及 CO 压力,研究了各种催化参数对苯乙烯转化成羰基化产物及其产物选择性的影响。通过适当选择吡啶亚胺配体的结构和反应参数,获得了高达 96 的转换数和高达 98%的二甲基苯基琥珀酸酯选择性。特别是苯乙烯的总体转化受亚胺芳基上烷基取代基的立体性质控制,而亚胺碳上的取代基(H 或 Me)的性质影响选择性。向催化混合物中加入 2 当量的 TsOH 通常会增加苯乙烯的转化率,但由于甲基 3,6-二苯基-4-氧代己酸酯的产量增加,降低了二甲基苯基琥珀酸酯的选择性。进一步添加 TsOH(高达 6 当量)使所有前体的选择性更好,转化率更低。
• Pyridinylimine-based nickel(II) and palladium(II) complexes: preparation, structural characterization and use as alkene polymerization catalysts
  作者：Timo V Laine、Ulla Piironen、Kristian Lappalainen、Martti Klinga、Erkki Aitola、Markku Leskelä

  DOI：10.1016/s0022-328x(00)00291-6

  日期：2000.7

  methyl-branched polymers. The effect of ligand environment was most evident on degree of branching, while catalytic activity and molecular weight of the polymer were more dependent on the general catalyst composition as well as reaction conditions. Activation of the dichloropalladium(II) complexes with MAO yields highly active catalysts for the polymerization of bicyclo[2.2.1]hept-2-ene (norbornene) whereas

  描述了四个二聚镍（II）配合物和三个带有二齿吡啶并嘧啶配体的单体钯（II）配合物的制备。这些化合物的固态结构已通过单晶X射线衍射确定。用甲基铝氧烷（MAO）活化后，镍化合物在乙烯聚合反应中用作催化剂，生成几乎线性或主要为甲基支化的聚合物。配体环境对支化度的影响最为明显，而聚合物的催化活性和分子量则更多地取决于一般催化剂的组成以及反应条件。用MAO活化二氯钯（II）配合物可产生用于双环[2.2.1]庚-2-烯（降冰片烯）聚合的高活性催化剂，而转化率很低（<4。
• Copolymerization of Ethylene and Methyl Acrylate by Pyridylimino Ni(II) Catalysts Affording Hyperbranched Poly(ethylene-<i>co</i>-methyl acrylate)s with Tunable Structures of the Ester Groups
  作者：Zeinab Saki、Ilaria D’Auria、Anna Dall’Anese、Barbara Milani、Claudio Pellecchia

  DOI：10.1021/acs.macromol.0c01703

  日期：2020.11.10

  considerable catalysts are based on Pd(II) complexes and only a few examples on Ni(II) derivatives have been reported. We have now investigated a series of Ni(II) complexes with four pyridylimino ligands, both aldimines and ketimines, differing for the substituent present in position 6 on the pyridine ring (either a methyl group or a 2,6-dimethyl-substituted phenyl ring). These complexes generated active catalysts

  向聚烯烃骨架中引入极性官能团是一项具有高度挑战性的挑战性目标，而配位插入聚合是实现这一目标的最有效，最环保的方法。迄今为止，最重要的催化剂是基于Pd（II）配合物的，仅报道了关于Ni（II）衍生物的一些实例。现在，我们研究了一系列带有四个吡啶亚胺基配体（醛亚胺和酮亚胺）的Ni（II）配合物，它们的吡啶环上6位上的取代基（甲基或2,6-二甲基取代的苯环）不同）。这些络合物生成了用于乙烯与丙烯酸甲酯共​​聚的活性催化剂，产生了极性单体含量为0的低分子量超支化共聚物。2和35 mol％并以多种模式插入，其中一些以前从未见过。极性单体的掺入方式来源于“仅在链中”到“链中所有位置都可以”，这取决于活化方式和用于溶解镍预催化剂的溶剂。
• Synthesis, structures of (aminopyridine)nickel complexes and their use for catalytic ethylene polymerization
  作者：Ya-Chi Lin、Kuo-Hsuan Yu、Ya-Fan Lin、Gene-Hsiang Lee、Yu Wang、Shiuh-Tzung Liu、Jwu-Ting Chen

  DOI：10.1039/c2dt30151b

  日期：——

  A series of α-aminopyridines in the form of (2,6-C6H3N)(R1)(CHR2NR3R4) (R1 = R2 = H R3 = H R4 = iPr (L1a), R4 = tBu (L1b), R4 = Ph (L1c), R4 = 2,6-Me2C6H3 (L1d), R4 = 2,6-iPr2C6H3 (L1e), R1 = R2 = H R3 = R4 = Et (L1f), R1 = H R2 = Me R3 = H R4 = iPr (L2a), R4 = Ph (L2c), R4 = 2,6-Me2C6H3 (L2d), R4 = 2,6-iPr2C6H3 (L2e), R1 = Me R2 = H R3 = H R4 = 2,6-iPr2C6H3 (L3e)) and β-aminopyridines in the form of (2-C6H4N)(CH2CH2NR1R2) (R1 = H R2 = iPr (4a), R2 = tBu (L4b), R1 = R2 = Et (L4f)) have been prepared. Their corresponding halonickel complexes 1a–4f are synthesized by ligand substitution from (DME)NiBr2 and the molecular structures are characterized. Four types of coordination modes include four-coordinate mononuclear species with one ligand, five-coordinate mononuclear species with two ligands, five-coordinate dinuclear species with two ligands, and a six-coordinate polymeric framework were determined by X-ray crystallography. Using methylaluminoxanes (MAO) as the activator, the nickel complexes can catalyze ethylene polymerization under moderate pressure and ambient temperature. The activity reaches 105 g PE mol−1 Ni h. The PE products with high branching and high crystallinity have Mn ∼ 103 with PDI < 2.

  一系列α-氨基吡啶类化合物(2,6-C6H3N)(R1)(CHR2NR3R4)(R1 = R2 = H, R3 = H, R4 = iPr (L1a), R4 = tBu (L1b), R4 = Ph (L1c), R4 = 2,6-Me2C6H3 (L1d), R4 = 2,6-iPr2C6H3 (L1e), R1 = R2 = H, R3 = R4 = Et (L1f), R1 = H, R2 = Me, R3 = H, R4 = iPr (L2a), R4 = Ph (L2c), R4 = 2,6-Me2C6H3 (L2d), R4 = 2,6-iPr2C6H3 (L2e), R1 = Me, R2 = H, R3 = H, R4 = 2,6-iPr2C6H3 (L3e))和β-氨基吡啶类化合物(2-C6H4N)(CH2CH2NR1R2)(R1 = H, R2 = iPr (4a), R2 = tBu (L4b), R1 = R2 = Et (L4f))已被合成。通过配体取代反应从(DME)NiBr2合成相应的卤化镍配合物1a–4f,并由X射线晶体学表征其分子结构。通过X射线结晶学确定了四种配位模式,包括单核四配位物种与一个配体、单核五配位物种与两个配体、双核五配位物种与两个配体以及六配位的聚合框架。使用甲基铝氧烷(MAO)作为活化剂,镍配合物可以在中等压力和室温下催化乙烯聚合。活性达到105 g PE mol−1 Ni h。具有高度支化和高度结晶性的PE产品,Mn ∼ 103,PDI < 2。
• New (Anilidomethyl)pyridine Titanium(IV) and Zirconium(IV) Catalyst Precursors for the Highly Chemo- and Stereoselective <i>cis</i>-1,4-Polymerization of 1,3-Butadiene
  作者：Liana Annunziata、Stefania Pragliola、Daniela Pappalardo、Consiglia Tedesco、Claudio Pellecchia

  DOI：10.1021/ma1028455

  日期：2011.4.12

  methylalumoxane (MAO) were tested in 1,3-butadiene and α-olefins polymerization. The zirconium complexes showed higher activity with respect to the titanium homologous. Polymerization of ethylene resulted, in all cases in the production of high molecular weight linear polyethylene. Propylene polymerization tests provided substantially atactic polypropylene. 1,3-Butadiene polymerizations produced cis-1,4

  已经合成了带有苯胺基甲基吡啶配体的第4组金属配合物，并通过核磁共振（NMR）光谱，元素分析和单晶X射线衍射分析对其进行了表征。在使用Al i Bu 2 H和甲基铝氧烷（MAO）活化后，所有配合物均在1,3-丁二烯和α-烯烃聚合反应中进行了测试。锆配合物相对于钛同源物显示出更高的活性。在所有情况下，乙烯的聚合导致高分子量线性聚乙烯的生产。丙烯聚合测试提供了基本上无规的聚丙烯。1,3-丁二烯聚合反应生成顺式-1,4聚丁二烯，在锆配合物的情况下，聚合物的含量为提供了更高的顺式-1,4个单位（99.9％）。催化剂的活性和立体选择性与配合物的空间特征有关。