4,4'-methylenebis(3,5-dimethylpyrazole) | 83524-76-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4,4'-methylenebis(3,5-dimethylpyrazole)
• 英文别名: bis(3,5-dimethyl-1H-pyrazol-4-yl)methane；bis(3,5-dimethyl-4-pyrazolyl)methane；1,1'-bis(3,5-dimethyl-1H-pyrazol-4-yl)methane；1H-Pyrazole, 4,4'-methylenebis[3,5-dimethyl-；4-[(3,5-dimethyl-1H-pyrazol-4-yl)methyl]-3,5-dimethyl-1H-pyrazole
• CAS: 83524-76-9
• 化学式: C₁₁H₁₆N₄
• 分子量: 204.275
• InChiKey: YCVRIOKURDSNRO-UHFFFAOYSA-N

物化性质

• 熔点：
  299-301 °C
• 沸点：
  448.0±40.0 °C(Predicted)
• 密度：
  1.153±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  57.4
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4'-methylenebis(3,5-dimethylpyrazole) 、 氯化苄 在 sodium hydroxide 、 四丁基溴化铵 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以79%的产率得到1,1'-dibenzyl-3,3',5,5'-tetramethyl-4,4'-methylenebis-pyrazole
  参考文献：
  名称：

  Binuclear pyrazoles. I. Synthesis and cytotoxic activity of 1,1'-dibenzyl and 1,1'-dihydroxymethyl 4,4'-bispyrazoles.

  摘要：

  从 3, 3', 5, 5'-tetramethyl-4, 4'-bis-1 H-pyrazole, 3, 3', 5, 5'-tetramethyl-4, 4'-methylenebis-1 H-pyrazole 和 4, 4'-methylenebis-1 H-pyrazole 中得到了相应的 1, 1'-dibenzyl 和 1, 1'-dihydroxymethyl 衍生物。1H- 双吡唑的苄基化是在相转移条件下用氯化苄进行的。羟甲基化是在酸性或中性介质中用 37% 的甲醛水溶液进行处理。所有得到的产物都进行了细胞毒性评估，其中 1, 1'-dibenzyl-3, 3', 5, 5'-tetramethyl-4, 4'-bispyrazole 是一种强力细胞毒剂（ED50=7 μM）。

  DOI：

  10.1248/cpb.33.2535
• 作为产物：
  描述：

  1,1,2,2-Tetraacetylcyclopropane 在 一水合肼 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以51%的产率得到4,4'-methylenebis(3,5-dimethylpyrazole)
  参考文献：
  名称：

  Celli, Angela Maria; Lampariello, Lucia Raffaella; Chimichi, Stefano, Gazzetta Chimica Italiana, 1983, vol. 113, # 7/8, p. 427 - 432

  摘要：

  DOI：

文献信息

• Tiara[<i>n</i>]uril: A Glycoluril-Based Macrocyclic Host with Cationic Walls
  作者：Pradeep Kumar Chandrakumar、Rajni Dhiman、Clifford E. Woodward、Hasti Iranmanesh、Jonathon E. Beves、Anthony I. Day

  DOI：10.1021/acs.joc.8b02913

  日期：2019.4.5

  The synthesis of new cationic macrocyclic host molecules is described. These macrocycles are comprised of glycoluril oligomers linked to two pyrazolium groups, which form part of a cationic wall facing into their cavities. A number of derivatives have been prepared with an objective to increasing the cavity size, and each new product has been fully characterized. Preliminary investigations of pKas

  描述了新的阳离子大环主体分子的合成。这些大环由连接两个吡唑基的甘脲低聚物组成，两个吡唑基形成面对它们的腔的阳离子壁的一部分。为了增加型腔的尺寸，已经制备了许多衍生物，并且每种新产品都已得到充分表征。对Me 10 Tu [3] 2+的p K a s的初步研究和L-谷氨酰胺的相互作用表明，结合具有H键供体基团的阴离子分子的潜力。
• Novel Coordination Polymers with (Pyrazolato)-Based Tectons: Catalytic Activity in the Peroxidative Oxidation of Alcohols and Cyclohexane
  作者：Ivan Timokhin、Claudio Pettinari、Fabio Marchetti、Riccardo Pettinari、Francesca Condello、Simona Galli、Elisabete C. B. A. Alegria、Luísa M. D. R. S. Martins、Armando J. L. Pombeiro

  DOI：10.1021/acs.cgd.5b00083

  日期：2015.5.6

  Coupling five rigid or flexible bis(pyrazolato)-based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340–500 °C. As demonstrated by N2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135–1758 m2/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (i) the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 × 103) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cyclohexane, the latter value being higher than that granted by the current industrial process.

  通过将五种刚性或柔性双（吡唑并）基构造子与后期过渡金属离子偶联，我们分离出了 18 种配位聚合物（CPs）。通过热分析评估，所有这些配位聚合物都具有显著的热稳定性，其分解温度在 340-500 °C 之间。77 K 下的 N2 吸附测量结果表明，它们的朗缪尔比表面积在 135-1758 m2/g 之间，与粉末 X 射线衍射结构溶液法获得的多孔或致密聚合物结构一致。测试了两个具有代表性的 CPs 家族，它们由刚性或柔性间隔物构成，在以下两种情况下用作催化剂：(i) t-BuOOH 在微波辅助下无溶剂过氧化氧化醇；(ii) H2O2 在乙腈中将环己烷过氧化成环己醇和环己酮。与具有柔性间隔的氯化铜相比，具有刚性间隔的氯化铜具有更高的比表面积，活性更高。此外，所研究的两种含铜（I）的氯化石蜡在这两种反应中都表现出了最高的效率，在氧化 1-苯基乙醇和氧化环己烷时，前者的选择性最高产物收率分别为 92%（TON 高达 1.5 × 103）和 11%，后者高于当前工业工艺的收率。
• Construction of coordination polymers based on methylenebis(3,5-dimethylpyrazole) and varied aromatic carboxylic acids
  作者：Xiang-Guang Guo、Wen-Bin Yang、Xiao-Yuan Wu、Qi-Kai Zhang、Can-Zhong Lu

  DOI：10.1039/c3ce41575a

  日期：——

  Six new coordination polymers, namely, [Co(Cl-BDC)(H2MDP)]·0.5H2O (1), [Cd(Cl-BDC)(H2MDP)] (2), [Cd(OH-ip)(H2MDP)2]·H2O (3), [Mn(NO2-ip)(H2MDP)(H2O)] (4), [Cu(BTEC)1/2(H2MDP)] (5), and [Co(BTEC)1/2(H2MDP)]·H2O (6) (H2MDP = methylenebis(3,5-dimethylpyrazole), Cl-H2BDC = 2,5-dichloroterephthalic acid, OH-H2ip = 5-hydroxy-1,3-benzenedicarboxylic acid, NO2-H2ip = 5-nitro-1,3-benzenedicarboxylic acid, H4BTEC = 1,2,4,5-benzenetetracarboxylic acid) have been hydrothermally synthesized by using H2MDP as the main ligand and varying aromatic acids as auxiliary ligands, and characterized by single-crystal X-ray structure determination, FT-IR, elemental analysis, and powder X-ray diffraction. It was found that in complexes 2, 3, 4, and 6 the H2MDP ligands adopt a cis-conformation and tend to form M2L2-type metallocyclic units (SBU-1). These metallocyclic units further serve as linkers to connect the metal–aromatic carboxylate}n chains to form two-dimensional frameworks with different structural features and topologies, i.e. 2D 63-hcb network for 2, (4,4) net for 3, undulated 63-hcb layered framework for 4, and dual (3,4)-connected net for 6 with point (Schläfli) symbol of (4·62)2(42·62·82). In complexes 1 and 5, the H2MDP ligands adopt a trans-conformation, and tend to link metal–aromatic carboxylate}n chains into a higher dimensional framework, i.e. 3D triply interpenetrated dia network for 1 and dual (4,4)-connected double-layered structure for 5 with point (Schläfli) symbol of (54·62)(55·81)2. Moreover, the magnetic properties of complexes 1 and 6, and photoluminescent properties of 3 have also been investigated.

  六种新型配位聚合物，即[Co(Cl-BDC)(H2MDP)]-0.5H2O（1）、[Cd(Cl-BDC)(H2MDP)]（2）、[Cd(OH-ip)(H2MDP)2]-H2O（3）、[Mn(NO2-ip)(H2MDP)(H2O)]（4）、[Cu(BTEC)1/2(H2MDP)]（5）和[Co(BTEC)1/2(H2MDP)]-H2O（6）（H2MDP = 亚甲基双（3、5-二甲基吡唑），Cl-H2BDC = 2,5-二氯对苯二甲酸，OH-H2ip = 5-羟基-1,3-苯二甲酸，NO2-H2ip = 5-硝基-1、3-苯二甲酸，H4BTEC = 1,2,4,5-苯四甲酸），并以 H2MDP 作为主配体，以不同的芳香酸作为辅助配体，通过水热法合成了这些配合物，并通过单晶 X 射线结构测定、傅立叶变换红外光谱、元素分析和粉末 X 射线衍射对其进行了表征。研究发现，在复合物 2、3、4 和 6 中，H2MDP 配体采用顺式构象，并倾向于形成 M2L2 型金属环单元（SBU-1）。这些金属环单元进一步充当连接金属芳香族羧酸}n 链的连接体，形成具有不同结构特征和拓扑结构的二维框架，即 2 的二维 63-hcb 网络、3 的（4,4）网络、4 的波状 63-hcb 层状框架，以及 6 的双 (3,4) 连接网络，其点（Schläfli）符号为 (4-62)2(42-62-82)。在配合物 1 和 5 中，H2MDP 配体采用了反式构型，并倾向于将金属芳香族羧酸}n 链连接到一个更高维的框架中，即 1 的三维三互穿二维网络和 5 的双（4,4）连接双层结构，其点（Schläfli）符号为 (54-62)(55-81)2 。此外，还研究了复合物 1 和 6 的磁性以及 3 的光致发光特性。
• Three new POM-based compounds constructed by rigid thiabendazole and flexible bis(pyrazole) ligands: structures and properties for Hg²⁺ recognition
  作者：Aixiang Tian、Yali Ning、Yang Yang、Xue Hou、Jun Ying、Guocheng Liu、Juwen Zhang、Xiuli Wang

  DOI：10.1039/c5dt02420j

  日期：——

  The introduction of S atoms to ligands induces the properties for Hg²⁺ recognition of POM-based compounds.

  将S原子引入配体中可诱导基于POM化合物对Hg²⁺的识别性能。
• A potassium-encapsulated Preyssler-based structure modified by binuclear cyclic copper(II) clusters: photocatalytic and electrochemical properties
  作者：Ai-Xiang Tian、Yan Yang、Huai-Ping Ni、Gui-Ying Liu、Yu-Bo Fu、Meng-Le Yang、Guo-Cheng Liu、Jun Ying

  DOI：10.1007/s11243-018-00294-z

  日期：2019.5

  [Cu2(H2bdpm)2]4+ to form a 1D chain. Adjacent chains are further connected by abundant intermolecular forces to construct a 2D supramolecular framework. The photocatalytic and electrochemical properties of the complex have been investigated.Graphical abstract(1) The Preyssler-based POM-TMCs are rarely reported. (2) The K-encapsulated Preyssler anion is uncommonly observed in Preyssler-based compound. (3)

  通过使用灵活的配体 1,1'-双(3,5-二甲基-1H-吡唑酸盐)甲烷 (H2bdpm)，一种 K 封装的基于 Preyssler 的复合物，[Cu4(H2bdpm)4(H2O)10(H6KP5W30O110 )]·2(H2bdpm)·14H2O，已在水热条件下合成。单晶 X 射线衍射分析表明，该配合物含有罕见的 K 包封 Preyssler 阴离子，它们通过双核环状簇 [Cu2(H2bdpm)2]4+ 连接形成一维链。相邻的链通过丰富的分子间力进一步连接以构建二维超分子框架。对该配合物的光催化和电化学性能进行了研究。图文摘要(1) Preyssler基POM-TMCs的报道很少。(2) K 包封的 Preyssler 阴离子在基于 Preyssler 的化合物中不常见。(3) Preyssler 阴离子通过双核 CuII 簇连接形成一维链。(4)化合物1表现出光催化和电化学性质。

表征谱图