N,N-bis(pyrazol-1-ylmethyl)aniline | 85264-37-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N-bis(pyrazol-1-ylmethyl)aniline
• 英文别名: N,N-bis(1H-pyrazolyl-1-methyl)aniline；N,N-bis{(1-H-pyrazole-1-yl)methyl}aniline；N,N-bis((1H-pyrazol-1-yl)methyl)aniline；bis((3,5-dimethyl-1-pyrazolyl)methyl)(phenylamine)；N,N-[bis(1H-pyrazol-1)methyl]aniline；N,N-bis{(1-pyrazolyl)methyl}-aniline
• CAS: 85264-37-5
• 化学式: C₁₄H₁₅N₅
• 分子量: 253.307
• InChiKey: FZLRKSWBBOYDKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  38.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  iron(II) chloride tetrahydrate 、 N,N-bis(pyrazol-1-ylmethyl)aniline 以 乙醇 为溶剂， 反应 24.0h， 以77.5%的产率得到[(N,N-bis{(1-H-pyrazole-1-yl)methyl}aniline)Fe(μ-Cl)Cl]₂
  参考文献：
  名称：

  Synthesis, structure, and magnetic properties of the halide-bridged dimeric complex [(bpmaL1)Fe(μ-Cl)Cl]2

  摘要：

  Complexation of FeCl2 center dot 4H(2)O with N,N-Bis{(1-Hpyrazole-1-yl)methyl}aniline [bpmaL(1)] gave air-stable dichloro-bridged binuclear iron(II) species (1a) having five-coordinated iron, which was characterised by X-ray crystallography and magnetic susceptibility. The geometry at each iron centre of 1a is a distorted trigonal bipyramid with two equivalent half-molecules providing overall C-i symmetry. One of the pyrazolyl nitrogen atoms (N1) and a chlorine atom (Cl2)# form one apex of the distorted trigonal bipyramid. The magnetic parameters indicated only a weak antiferromagnetic coupling, despite the presence of two chloro ions, and dominant zero-field-splitting parameters. The relatively long Fe center dot center dot center dot Fe distance of 3.8118(6) angstrom within the chloro-bridged dimer excludes direct interaction between the iron(II) ions. Thus, the antiferromagnetic coupling between the two iron(II) ions of 1a is attributed to superexchange through the chloride ions. Compared to the analogous cobalt complexes, the activity of a-olefin polymerization towards ethylene, norbornene, 1-octene and methyl methacrylate (MMA) was virtually zero, 1a is the first bis-pyrazole based dinuclear and five-coordinated iron(II) complex. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2012.09.010
• 作为产物：
  描述：

  1-吡唑甲醇 、 苯胺 反应 72.0h， 生成 N,N-bis(pyrazol-1-ylmethyl)aniline
  参考文献：
  名称：

  N'-取代的N，N'，N-双（（1H-吡唑-1-基）甲基）胺衍生物负载的4-配位钴（II）配合物聚合甲基丙烯酸甲酯和rac-丙交酯

  摘要：

  因此导致形成八元螯合环。[LDCoCl2]在60°C的改性甲基铝氧烷（MMAO）存在下，对于甲基丙烯酸甲酯（MMA）的聚合反应表现出最高的催化活性（4.02×104 g PMMA / molCo h），并生成具有高分子量（Mw）（10.5×105 g / mol）。在123–130°C的温度范围内获得了富含间规的PMMA。在本研究中，配合物的MMA聚合活性不应仅视为金属中心周围配体的总位阻的函数。原位生成的二甲基衍生物[LnCoMe2]（Ln = LA-LH）有效地聚合了rac-丙交酯（rac-LA），并得到了具有良好的数均分子量和较窄的多分散指数（PDI）的聚丙交酯（PLA）。这些二甲基钴引发剂中金属中心周围的电子密度似乎增强了活性，而立体选择性受到了负面影响。因此，吡唑环部分中是否存在甲基不仅影响MMA聚合中Co（II）配合物的活性，而且影响rac-LA的ROP中Co（II）引发剂的立体选择性。

  DOI：

  10.1016/j.poly.2017.12.021

文献信息

• X‐ray crystal structures and MMA polymerization of cadmium(II) complexes with bidentate pyrazole ligands: the formation of monomers or dimers as a function of a methyl substituent on the pyrazole and aniline rings
  作者：Dongil Kim、Sunghoon Kim、Hyun Yul Woo、Ha‐Jin Lee、Hyosun Lee

  DOI：10.1002/aoc.3148

  日期：2014.6

  N,N‐bis(1H‐pyrazolyl‐1‐methyl)aniline (L1), N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐p‐methylaniline (L2), N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐3,5‐dimethylaniline (L3), N,N‐bis(3,5‐dimethyl‐1H‐pyrazolyl‐1‐methyl)aniline (L4) and N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐2,6‐dimethylaniline (L5) in ethanol yields novel Cd(II) bromide complexes, [L1CdBr2]2, [L2CdBr2]2, [L3CdBr2]2, [L4CdBr2] and [L5CdBr2]. The X‐ray crystal structures

  CdBr 2 ·4H 2 O与辅助配体N，N-双（1 H-吡唑基-1-甲基）苯胺（L 1），N，N-双（1 H-吡唑基-1-甲基）-反应对甲基苯胺（L 2），N，N-双（1 H-吡唑基-1-甲基）-3,5-二甲基苯胺（L 3），N，N-双（3,5-二甲基-1 H-吡唑基-1-甲基苯胺（L 4）和N，N-双（1 H-吡唑基-1-甲基）-2,6-二甲基苯胺（L 5）在乙醇中生成新型Cd（II）溴化物配合物[L 1 CdBr 2 ] 2，[L 2 CdBr 2 ] 2，[L 3 CdBr 2 ] 2，[L 4 CdBr 2 ]和[L 5 CdBr 2 ]。[L 1 CdBr 2 ] 2，[L 2的X射线晶体结构CdBr 2 ] 2和[L 3 CdBr 2 ] 2揭示了一种具有晶体学反演对称性的溴桥联二聚体。相反，[L 4 CdBr 2 ]和[L 5 CdBr 2 ]作为单体络合物存在，可能是由于[L
• Reibenspies, Joseph H.; Anderson, Oren P.; Eaton, Sandra S., Inorganic Chemistry, 1987, vol. 26, # 1, p. 132 - 137
  作者：Reibenspies, Joseph H.、Anderson, Oren P.、Eaton, Sandra S.、More, Kundalika M.、Eaton, Gareth R.

  DOI：——

  日期：——
• Synthesis and X-ray crystal structure of derivatives from the N,N-bis(1H-pyrazolyl-1-methyl)aniline(dichloro)Zn(II) complex: Substituent effects on the phenyl ring versus the pyrazole ring
  作者：Eunhee Kim、Hyun Yul Woo、Sunghoon Kim、Hajin Lee、Dongil Kim、Hyosun Lee

  DOI：10.1016/j.poly.2012.05.014

  日期：2012.7

  The reaction of anhydrous ZnCl2 with ancillary ligands, including N,N-bis(1H-pyrazolyl-1-methyl)aniline (L-1), N,N-bis(1H-pyrazolyl-1-methyl)-p-methoxyaniline (L-2), N,N-bis(1H-pyrazolyl-1-methyl)-p-fluoro-aniline (L-3) and N,N-bis(3,5-dimethyl-1H-pyrazolyl-1-methyl)aniline (L-4), in ethanol yields Zn(II) chloride complexes, i.e., L1ZnCl2, L2ZnCl2, L3ZnCl2 and L4ZnCl2. X-ray crystallographic analysis revealed that the Zn atoms of all of the synthesized complexes have a distorted tetrahedral geometry involving a nitrogen atom from each of two pyrazole groups and two chloro ligands. However, the nitrogen atom of the aniline group is not coordinated to the Zn center, resulting in the formation of an eight-membered chelate ring. The catalytic activity of the Zn(II) complexes in the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) results in a higher molecular weight and a narrow polydispersity index (PDI) range. (c) 2012 Elsevier Ltd. All rights reserved.
• Driessen, Willem L., Recueil des Travaux Chimiques des Pays-Bas, 1982, vol. 101, # 12, p. 441 - 443
  作者：Driessen, Willem L.

  DOI：——

  日期：——
• Synthesis, characterization, and MMA polymerization activity of tetrahedral Co (II) complex bearing N, N-bis(1-pyrazolyl)methyl ligand based on aniline moiety
  作者：Minkyu Yang、Won Jin Park、Keun Byoung Yoon、Jong Hwa Jeong、Hyosun Lee

  DOI：10.1016/j.inoche.2010.10.019

  日期：2011.1

  A new series of air-stable Co(II) complexes, [bpmaL1)CoCl2 (la), [bpmaL2]CoCl2 (2a), [bpmaL3]CoCl2 (3a), and [bpmaL4]CoCl2 (4a), where, for example, [bpmaL1 = N,N-bis(1-pyrazolyl)methyl}aniline], has been synthesized. X-ray crystallography of 2a indicated that it has a dipper-type structure in which the aniline moiety plays the role of the handle with a tetrahedral cobalt located at the edge with an eight-membered chelate ring formation. However, there is no indication that the metal is coordinated to the nitrogen of the aniline group. Moreover, complexes showed the highest catalytic activity in the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) with an activity of 1.14 x 10(6) g PMMA/mol-Co center dot h at 60 degrees C and syndiotacticity of PMMA, characterized by C-13 NMR spectroscopy, which value was ca. 0.57. (c) 2010 Elsevier B.V. All rights reserved.