2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole | 1392137-84-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole
• 英文别名: 1-[[5-[(3,5-dimethylpyrazol-1-yl)methyl]-1H-pyrrol-2-yl]methyl]-3,5-dimethylpyrazole
• CAS: 1392137-84-6
• 化学式: C₁₆H₂₁N₅
• 分子量: 283.376
• InChiKey: JPPBVFFIBWIEAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  51.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 在 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 2,5-bis{di(3,5-dimethylpyrazolyl)methene}-2,5-dihydropyrrole
  参考文献：
  名称：

  未取代的醌型吡咯及其通过DDQ氧化与氧气，电荷转移和钯（ii）配合物的反应†

  摘要：

  2,5-双（3,5-二甲基吡唑基甲基）吡咯与2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）的脱氢反应，然后用碳酸氢钠处理，得到两种含氧的新产物原子2，5-双（3，5-二甲基吡唑基羰基）吡咯（2）和5- {双-（3，5-二甲基吡唑基）甲基}吡咯-2-甲醛（3）。有趣的是，当反应混合物未用碱处理时，产物是不同的。它们是2，2-三（3,5- dimethylpyrazolylmethyl）-5-（3,5- dimethylpyrazolylcarbonyl）吡咯（4）和所述加合物5中，2,3-二氯-5,6-二氰基（DDQH 2）加合物2,5-双{二（3,5-二甲基吡唑基）亚甲基} -2,5-二氢吡咯（6）分离，产率为22％，其中6用作电子受体，DDQH 2用作电子供体。用NaBH 4或碱性氧化铝处理5可以得到高产率的游离碱6，代表了吡咯的离散的未取代醌型结构。6是荧光的，反应性的并且可以具

  DOI：

  10.1039/c4ra07808j
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 1,1'-(1H-pyrrole-2,5-diyl)bis(N,N,N-trimethylmethanaminium) diiodide 在 potassium hydroxide 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以47%的产率得到2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole
  参考文献：
  名称：

  Pyrrole pincers containing imidazole, pyrazole and 1,2,4-triazole groups

  摘要：

  Pincer compounds containing a central pyrrole linked through methylene groups in the 2,5-positions to two N-imidazole, N-pyrazole and N-1,2,4-triazole heterocyles have been prepared via a common quaternary amine precursor. Alkylation of the imidazole groups using methyl iodide or benzyl bromide gave imidazolium compounds. The methylated iodide salt was characterised crystallographically, showing significant pyrrole I center dot center dot center dot HN, imidazolium I center dot center dot center dot HC and imidazolium I center dot center dot center dot(sp(2)-C) interactions leading to a U-shaped conformation of the cationic pincer compound. The alkylated cations which were investigated as precursors to pyrrole-carbene pincer ligands, but all attempts to either coordinate palladium or deprotonate using silver oxide led to cleavage of the heterocycles from the central pyrrole. The result was the formation of palladium and silver complexes containing 3-N-methylimidazole (3-N-MeIm) or 3-N-benzylimidazole (3-N-BzIm) ligands: (3-N-MeIm)PdI2, (3-N-MeIm)PdCl2 and [(3-N-MeIm)(2)Ag]I, with the (3-N-MeIm)PdI2 complex characterised by crystallography. Pyrazole, 3,5-dimethylpyrazole and 1,2,4-triazole pincer compounds were prepared, the latter characterised by a molecular structure determination. The pyrazole and 1,2,4-triazole pincers coordinate directly to palladium through the deprotonated central pyrrolyl and neutral N-donors on the flanking heterocycles. (C) 2014 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.07.022

文献信息

• Mononuclear, helical binuclear palladium and lithium complexes bearing a new pyrrole-based NNN-pincer ligand: fluxional property
  作者：Debasish Ghorai、Shanish Kumar、Ganesan Mani

  DOI：10.1039/c2dt30816a

  日期：——

  A new pyrrole based NNN-pincer ligand, 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2, was readily synthesized in two steps from pyrrole in 56% yield. The lithiation of the pincer ligand 2 using n-BuLi led to isolation of the dimeric lithium complex, [Liμ-C4H2N-2,5-(CH2Me2pz)2-N,N,N}]24, in 23% crystalline yield. The transmetalation reaction of 4 with [Pd(PhCN)2Cl2] afforded the mononuclear Pd(II) complex, [PdClC4H2N-2,5-(CH2Me2pz)2-N,N,N}] 5, containing one chloride ion in 45% yield. Alternatively 5 was obtained in an excellent yield of 87% by the reaction of 2 with [Pd(COD)Cl2] in the presence of triethylamine. On the contrary, a 20-membered macrometalacyclic molecule, [Pd2Cl4μ-C4H3N-2,5-(CH2Me2pz)2-N,N}2] 6, in which two PdCl2 units are bridged by two molecules of 2 to give a helical structure, was synthesized by the reaction of 2 with [Pd(COD)Cl2] in the absence of base. The acetate analogue of complex 5, [Pd(OAc)C4H2N-2,5-(CH2Me2pz)2-N,N,N}] 3, was obtained by the treatment of 2 with [Pd(OAc)2]. The pyrrole twist angle of 5 is higher than that of 3. Complexes 3 and 5 show an AB pattern for their methylene protons at room temperature in CDCl3 as well as in DMSO-d6. The variable temperature NMR studies showed that the acetate and chloride complexes exhibit slightly different coalescence temperatures, which is a solvent dependent phenomenon, and twist angles.

  一种基于吡咯的新型NNN夹心配体，2,5-双(3,5-二甲基吡唑基甲基)吡咯2，经过两步反应从吡咯中合成，产率为56%。使用n-BuLi对夹心配体2进行锂化，得到二聚锂络合物[Liμ-C4H2N-2,5-(CH2Me2pz)2-N,N,N}]24，晶体产率为23%。与[Pd(PhCN)2Cl2]的转金属反应生成一核Pd(II)络合物[PdClC4H2N-2,5-(CH2Me2pz)2-N,N,N}]5，含有一个氯离子，产率为45%。另外，通过将2与[Pd(COD)Cl2]在三乙胺存在下反应，可以以优良的87%产率获得5。相反，20元大环金属分子[Pd2Cl4μ-C4H3N-2,5-(CH2Me2pz)2-N,N}2]6是在没有碱的情况下通过将2与[Pd(COD)Cl2]反应合成的，其中两个PdCl2单元通过两分子2桥接，形成螺旋结构。复合物5的醋酸盐类似物[Pd(OAc)C4H2N-2,5-(CH2Me2pz)2-N,N,N}]3是通过将2与[Pd(OAc)2]处理获得的。复合物5的吡咯扭转角高于3。在室温下，复合物3和5在CDCl3和DMSO-d6中均显示出其亚甲基质子的AB模式。可变温度核磁共振研究表明，醋酸盐和氯化物络合物的融合温度略有不同，这是一个依赖于溶剂的现象，以及其扭转角度。
• New types of Cu and Ag clusters supported by the pyrrole-based NNN-pincer type ligand
  作者：Oishi Jana、Ganesan Mani

  DOI：10.1039/c7nj01009e

  日期：——

  coordination polymer of the type [Ag(μ-C4H3N-2,5-(CH2Me2pz)2-N,N)(X)]n where X = CF3SO3− 4a or BF4− 4b. Conversely, a new trinuclear silver(I) complex [Ag3(μ-C4H2N-2,5-(CH2Me2pz)2-N,N,N)3] 5 was obtained when the reaction was carried out with the lithium salt of LH and AgBF4. The structures of 1b, 1c, 3, 4a and 5 were confirmed by single crystal X-ray diffraction studies and supported by NMR, FTIR, HRMS

  2，5-双（3，5-二甲基吡唑基甲基）吡咯LH在吡咯NH质子去质子化时成为单阴离子NNN夹钳配体。它不仅提供典型的钳型配合物，而且通过其桥联配合模式支持多核配合物。一系列铜（I）和银（I）配合物的合成和表征证明了这一点。之间的反应LH和的CuX，其中X = Cl，Br和I，得到式[铜的双核配合物2（μ-X）2（μ-C 4 H ^ 3的N- 2,5-（CH 2我2 PZ ）2 - ñ，N）2 ]（1a–c）。相反地，当反应用的锂盐进行LH和CuI，一种新颖的四核铜（我）络合物[铜4（μ-I）2（μ-C 4 H ^ 2的N- 2,5-（CH 2箱2 PZ）2 - ñ，ñ，ñ）2 ] 2而获得，其核心结构相似的“沙漏”。用氯化亚铜或溴化亚铜的类似的反应，得到中性铜（II）配合物[铜（μ-C 4 H ^ 2N-2,5-（CH 2 Me 2 PZ）2 - N，N，N）2 ] 3在空气中氧化时，其中L