四(4-吡啶甲氧基)甲烷 | 163629-49-0

• 物质功能分类: 医药中间体 - 吡啶类化合物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 四(4-吡啶甲氧基)甲烷
• 英文名称: tetrakis(4-pyridyloxymethylene)methane
• 英文别名: tetrakis(4-pyridyloxymethyl)methane；tpom；4,4'-((2,2-Bis((pyridin-4-yloxy)methyl)propane-1,3-diyl)bis(oxy))dipyridine；4-[3-pyridin-4-yloxy-2,2-bis(pyridin-4-yloxymethyl)propoxy]pyridine
• CAS: 163629-49-0
• 化学式: C₂₅H₂₄N₄O₄
• 分子量: 444.49
• InChiKey: OTPHKFZNHRRWOG-UHFFFAOYSA-N

物化性质

• 熔点：
  198 °C
• 沸点：
  640.6±50.0 °C(Predicted)
• 密度：
  1.243±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  33
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  8

安全信息

• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P305+P351+P338,P330,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  应存于室温、密封、干燥且惰性气体环境中。

反应信息

• 作为反应物：
  描述：

  四(4-吡啶甲氧基)甲烷 以 二氯甲烷 、 乙腈 为溶剂， 生成 [Cu(I)(tetrakis[(pyridin-4-yloxy)methyl]methane)(BF4)]*MeCN*2H2O
  参考文献：
  名称：

  Engineering New Metal-Organic Frameworks Built from Flexible Tetrapyridines Coordinated to Cu(II) and Cu(I)

  摘要：

  A series of new metal-organic frameworks have been constructed by the coordination of Cu(II) and Cu(I) with pentaerythrityl tetrakis(4-pyridyl) ether (1 = PETPE), a flexible tetradentate ligand. Networks derived from Cu(OOCCH3)(2), Cu(NO3)(2), and CuBF4 proved to have different topologies (diamondoid, PtS, and SrAl2, respectively). This reflects (1) the ability of PETPE (1) to adopt diverse conformations and (2) the varied geometries of complexes of Cu(II) and Cu(I). Extended PETPE (2), a tetrapyridine with phenyl spacers inserted into the pentaerythrityl core of PETPE (1), yielded an expanded version of the PtS network derived from simple PETPE (1) and Cu(NO3)(2). However, increases in the ability of the network to accommodate guests were largely offset by interpenetration of independent networks. Attempts to thwart interpenetration by converting ligand 2 into methyl-substituted derivative 3 led to the construction of networks with alternative topologies. In particular, the reactions of ligand 3 with both Cu(II) and Cu(I) yielded isostructural Pt3O4 networks, despite the preference of the two oxidation states for coordination spheres with different geometries. Together, these observations demonstrate that PETPE (1) and related compounds are useful ligands for constructing metal-organic frameworks, with a distinctive ability to accommodate a single metal in different oxidation states, as well as to adapt to a metal in a single oxidation state but with different counterions or secondary ligands.

  DOI：

  10.1021/ic8019809
• 作为产物：
  描述：

  4-氯吡啶 、 季戊四醇 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 24.67h， 以90%的产率得到四(4-吡啶甲氧基)甲烷
  参考文献：
  名称：

  由N ... I卤素键支持的高度互穿的超分子网络。

  摘要：

  卤素键（XB）已用于将四（4-吡啶基）季戊四醇（四齿XB受体）与不同的α，ω-二碘全氟代烷烃（双齿XB供体）或四（4-碘四氟苯基）季戊四醇（四齿XB供体）组装。XB形成的非凡线性，α，ω-二碘全氟烷烃的棒状特征和季戊四醇分子之间的互补性将XB受体的三维特征转化为开放的主要网络，这些网络相互渗透以避免空隙的出现，并且确保模块隔离。已获得具有四重和五重互穿的二维（2D）正方形4（4）层（sql），以及Ia类的八倍菱形网络（dia）和显着的IIIa类十倍直径网络。

  DOI：

  10.1002/chem.200601653

文献信息

• Multitopic ligand directed assembly of low-dimensional metal-chalcogenide organic frameworks
  作者：Yi Liu、Kaiqi Ye、Yue Wang、Qichun Zhang、Xianhui Bu、Pingyun Feng

  DOI：10.1039/c6dt04453k

  日期：——

  that compounds NTU-2, NTU-3 and NTU-4 possess two-dimensional layer structures, while compound NTU-1 adopts a one-dimensional coordination framework (NTU-n, where n is the number related to a specific structure). The diffuse-reflectance spectra demonstrate that these four compounds possess indirect bandgaps and their tunable bandgaps are correlated with their compositions and crystal structures.

  尽管金属有机框架取得了巨大进展，但金属硫属化物有机框架仅取得了有限的成功。金属硫属化物有机骨架是可取的，因为它们提供了通往可调谐半导体多孔骨架的有前途的途径。在这里，已经通过溶剂热法合成了四种新颖的硫族化物-有机杂化化合物。多位有机分子，即1,2-二-（4-吡啶基）乙烯（L 1），1,3,5-三（4-吡啶基-反式乙烯基）苯（L 2）和四（4-吡啶基甲醛））甲烷（L 3），已用作连接器来组装Zn（SAr）2或Zn 2（SAr）4个单元生成不同的空间组织模式。单晶结构分析表明，化合物NTU-2， NTU-3和NTU-4具有二维层结构，而化合物NTU-1采用一维配位构架（ NTU- n，其中n是与特定的结构）。漫反射光谱表明，这四种化合物具有间接带隙，并且它们的可调带隙与它们的组成和晶体结构相关。
• Syntheses, characterization, and properties of five coordination compounds based on the ligand tetrakis(4-pyridyloxymethylene)methane
  作者：Zemin Ju、Dapeng Cao、Ling Qin、Chuanlei Zhang、Mingdao Zhang、Zhiqiang Shi、Hegen Zheng

  DOI：10.1039/c3ce42477d

  日期：——

  Based on tetrakis(4-pyridyloxymethylene)methane (TPOM) and different carboxylates, five new MOFs with structures of high dimension and mutual interpenetration have been successfully synthesized.

  基于四(吡啶氧甲醛)甲烷(TPOM)和不同的羧酸盐，成功合成了五种具有高维结构和相互穿插的新型MOF。
• Photochemical and Magnetic Properties of Seven New Metal–Organic Frameworks Constructed by Flexible Tetrapyridines and V-Shaped Polycarboxylate Acids
  作者：Jin-Song Hu、Xin-Hua Huang、Cheng-Ling Pan、Lei Zhang

  DOI：10.1021/acs.cgd.5b00067

  日期：2015.5.6

  Seven two- or three-dimensional (2D or 3D) coordination polymers have been synthesized by tetrakis(4-pyridyloxymethylene)methane (TPOM) with V-shaped 4,4′-oxybis(benzoicacid) (H2oba), 4,4′-sulfonyldibenzoic acid (H2sdb), 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), 4,4′-dicarboxydiphenylamine (H2ddpa), and 4,4′-dicarboxy-ethyl diphenylamine (H2dedpa) in the presence of nitrates of transition metal in H2O/DMF systems, namely, [Co2(TPOM)(oba)2(H2O)2]·(H2O)8}n (1), [Cd2(TPOM)(oba)2(H2O)2]·(H2O)4(DMF)1.5}n (2), [Ni2(TPOM)(oba)2(H2O)2]·(H2O)5}n (3), [Co2(TPOM)(hfipbb)2]·(H2O)3}n (4), [Cd2(TPOM)(dedpa)2]·(H2O)4(DMF)2}n (5), [Co2(TPOM)(sdb)2]·(H2O)3}n (6), [Co2(TPOM)(ddpa)2]}n (7). Complexes 1–3 have similar structures, possessing 3D self-penetrated frameworks. Complex 4 is also a self-penetrated 3D framework containing meso-helix [Co(hfipbb)]n chains. Complex 5 reveals a 2-fold interlocked 2D → 2D network. For complex 6, only three pyridyl groups coordinated to Co(II) ions in one TPOM ligand, while for complex 7, only two pyridyl groups coordinated to Co(II) ions in one TPOM ligand. In addition, magnetic, fluorescence, and UV–vis properties of these complexes have been studied.

  通过四（4-吡啶氧基甲烷）甲烷（TPOM）与V型的4,4'-氧双（苯甲酸）（H2oba）、4,4'-磺酰基二苯甲酸（H2sdb）、4,4'-(六氟异丙烯基)双（苯甲酸）（H2hfipbb）、4,4'-二羧基二苯胺（H2ddpa）和4,4'-二羧基乙基二苯胺（H2dedpa）在水/二甲基甲酰胺（DMF）体系中与过渡金属硝酸盐的存在下，合成了七种二维或三维（2D或3D）配位聚合物，即[Co2(TPOM)(oba)2](H2O)2·( )8}n（1），[Cd2(TPOM)(oba)2]( )2·( )4(DMF)1.5}n（2），[Ni2(TPOM)(oba)2]( )2·( )5}n（3），[Co2(TPOM)(hfipbb)2]·( )3}n（4），[Cd2(TPOM)(dedpa)2]·( )4(DMF)2}n（5），[Co2(TPOM)(sdb)2]·( )3}n（6），[Co2(TPOM)(ddpa)2]}n（7）。复合物1-3具有相似的结构，拥有三维自穿透框架。复合物4也是一个自穿透的三维框架，包含有序螺旋[Co(hfipbb)]n链。复合物5呈现出双重交锁的二维 → 二维网络。对于复合物6，仅有三个吡啶基团与一个TPOM配体中的Co(II)离子配位，而对于复合物7，仅有两个吡啶基团与一个TPOM配体中的Co(II)离子配位。此外，还研究了这些复合物的磁性、荧光和紫外-可见光性质。
• Thermally Induced and Photoinduced Valence Tautomerism in a Two-Dimensional Coordination Polymer
  作者：Bao Li、Li-Qin Chen、Rong-Jia Wei、Jun Tao、Rong-Bin Huang、Lan-Sun Zheng、Zhiping Zheng

  DOI：10.1021/ic102270h

  日期：2011.1.17

  Herein reported is the first two-dimensional coordination polymer capable of undergoing thermally induced and photoinduced valence tautomeric transitions.

  本文报道的是第一种能够经历热诱导和光诱导化合价互变异构转变的二维配位聚合物。
• Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution
  作者：Georges Mouchaham、Nans Roques、Walid Khodja、Carine Duhayon、Yannick Coppel、Stéphane Brandès、Tamás Fodor、Michel Meyer、Jean-Pascal Sutter

  DOI：10.1002/chem.201701732

  日期：2017.9.4

  solvent‐accessible void (53 %). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good selectivity of the porous material for the halogenated acids. The gathered results, including a series of guest@SPA‐2 crystal structures

  通过电荷化学计量组装质子化的四（4-吡啶氧基氧基甲基）甲烷和[Al（草酸酯）3 ] 3−（它们是氢键的供体和受体），构建了一个带有吡啶基修饰孔的氢键开放骨架。离子氢键相互作用。这种超分子多孔结构（SPA-2）的1D大孔在3D中相互连接，并带有大的溶剂可触及的空隙（53％）。它对溶液中的酸性有机分子表现出显着的亲和力，已通过各种羧酸（包括较大的药物分子）进行了研究。乙酸与其卤代同系物之间的竞争性吸附证明了多孔材料对卤代酸的良好选择性。收集的结果，包括一系列的guest @ SPA-2晶体结构和HRMAS-NMR光谱，表明该材料表现出的有效吸附不仅取决于酸碱相互作用。这些客体分子在中性条件下的轻松释放使该SPA成为酸性分子的载体。