5,15-Bis(4-ethynylphenyl)-5,10,10,15,20,20-hexamethyl-21,22,23,24-tetrahydroporphyrin | 1369591-88-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 5,15-Bis(4-ethynylphenyl)-5,10,10,15,20,20-hexamethyl-21,22,23,24-tetrahydroporphyrin
• CAS: 1369591-88-7
• 化学式: C₄₂H₄₀N₄
• 分子量: 600.806
• InChiKey: AQKFSMNFHDLPQW-UHFFFAOYSA-N

物化性质

• 沸点：
  710.6±60.0 °C(predicted)
• 密度：
  1.24±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  46
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  63.2
• 氢给体数：
  4
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5,15-Bis(4-ethynylphenyl)-5,10,10,15,20,20-hexamethyl-21,22,23,24-tetrahydroporphyrin 在 4,4'-二吡啶-N,N'-二氧二水合物 、 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 3.25h， 以60%的产率得到1,14,19,19,24,37,42,42,51,51,68,68-Dodecamethyl-56,57,58,59,73,74,79,80-octazapentadecacyclo[35.9.9.914,24.22,5.210,13.225,28.233,36.115,18.120,23.138,41.143,46.147,50.152,55.164,67.169,72]octaconta-2(78),3,5(77),10,12,15,17,20,22,25(63),26,28(62),33(61),34,36(60),38,40,43,45,47,49,52,54,64,66,69,71,75-octacosaen-6,8,29,31-tetrayne
  参考文献：
  名称：

  Polyatomic Anion Assistance in the Assembly of [2]Pseudorotaxanes

  摘要：

  We describe the use, of polyatomic anions for the quantitative assembly of ion-paired complexes displaying pseudorotaxane topology. Our approach exploits the unique ion-pair recognition properties exhibited by noncovalent neutral receptors assembled through hydrogen-bonding interactions between a bis-calix[4]pyrrole macro cycle and linear bis-amidepyridyl-N-oxides. The complexation of bidentate polyatomic anions that are complementary in size and shape to the receptor's cavity, in which six NH hydrogen-bond donors converge, induces the exclusive formation of four particle-threaded assemblies.

  DOI：

  10.1021/ja301900s
• 作为产物：
  描述：

  在 sodium hydroxide 作用下， 以 甲苯 为溶剂， 反应 3.5h， 以100%的产率得到5,15-Bis(4-ethynylphenyl)-5,10,10,15,20,20-hexamethyl-21,22,23,24-tetrahydroporphyrin
  参考文献：
  名称：

  Polyatomic Anion Assistance in the Assembly of [2]Pseudorotaxanes

  摘要：

  We describe the use, of polyatomic anions for the quantitative assembly of ion-paired complexes displaying pseudorotaxane topology. Our approach exploits the unique ion-pair recognition properties exhibited by noncovalent neutral receptors assembled through hydrogen-bonding interactions between a bis-calix[4]pyrrole macro cycle and linear bis-amidepyridyl-N-oxides. The complexation of bidentate polyatomic anions that are complementary in size and shape to the receptor's cavity, in which six NH hydrogen-bond donors converge, induces the exclusive formation of four particle-threaded assemblies.

  DOI：

  10.1021/ja301900s

文献信息

• Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts
  作者：Qingqing Sun、Gemma Aragay、Andrea Pinto、Elisabet Aguiló、Laura Rodríguez、Pablo Ballester

  DOI：10.1002/chem.201905160

  日期：2020.3.12

  We report the synthesis of an unprecedented mono-gold(I) phosphine complex based on a "two-wall" aryl-ethynyl extended calix[4]pyrrole. We describe and compare the binding properties of the parent 10α,20α-bis-aryl-ethynyl calix[4]pyrrole ligand and the prepared organometallic compound as receptors for tetraalkylammonium chloride salts in dichloromethane and acetone. We describe the results of 1 H NMR

  我们报告了基于“两壁”芳基-乙炔基扩展杯[4]吡咯的前所未有的单金（I）膦配合物的合成。我们描述并比较了母体10α，20α-双芳基-乙炔基杯[4]吡咯配体和制备的有机金属化合物作为二氯甲烷和丙酮中四烷基氯化铵盐受体的结合性能。我们描述了在二氯甲烷和丙酮中的1 H NMR，UV-Vis滴定和等温滴定量热（ITC）实验的结果，旨在热力学表征所形成的配合物。获得的结果表明，与母体配体2相比，氯化物对单金（I）受体1的结合亲和力明显降低。
• Switching from Negative-Cooperativity to No-Cooperativity in the Binding of Ion-Pair Dimers by a Bis(calix[4]pyrrole) Macrocycle
  作者：Ricardo Molina-Muriel、Gemma Aragay、Eduardo C. Escudero-Adán、Pablo Ballester

  DOI：10.1021/acs.joc.8b02449

  日期：2018.11.2

  We report the synthesis of a macrocyclic receptor containing two di-meso-phenylcalix[4]pyrrole units linked by two triazole spacers. The 1,4-substitution of the 1,2,3-triazole spacers conveys different binding affinities to the two heteroditopic binding sites. These features make the receptor an ideal candidate to investigate allosteric cooperativity in the binding of ion-pair dimers. We probed the

  我们报告了一个大环受体的合成，该受体含有两个由两个三唑间隔基连接的二-内消旋-苯基杯[4]吡咯单元。1,2,3-三唑间隔基的1,4-取代基将不同的结合亲和力传递至两个异位结合位点。这些特征使该受体成为研究离子对二聚体结合中的变构协同作用的理想候选者。我们使用探测在氯仿溶液四烷基铵盐与四异位大环受体的相互作用（TBA·氯，TBA·OCN，和MTOA·Cl）的11 H NMR光谱滴定实验。获得的结果表明，在毫摩尔浓度下，向受体溶液中加入2当量的盐会诱导离子对的定量成对结合。2：1（离子对：受体）络合物的特征在于不同的结合几何形状和结合协同能力，具体取决于烷基铵阳离子的性质。单晶的X射线衍射分析完全支持了分配给溶液中离子对二聚体络合物的结合几何形状。结合过程的热力学特征（分别形成或同时形成1：1和2：1的复合物），是根据等温滴定热（ITC）实验得出的，
• Highly Cooperative Binding of Ion-Pair Dimers and Ion Quartets by a Bis(calix[4]pyrrole) Macrotricyclic Receptor
  作者：Virginia Valderrey、Eduardo C. Escudero-Adán、Pablo Ballester

  DOI：10.1002/anie.201302524

  日期：2013.7.1

  Connect four: A macrotricyclic receptor equipped with two convergent calix[4]pyrrole units features unprecedented binding properties towards two ion pairs. A highly cooperative binding process is observed for pairs of tetrabutylammonium (TBA) salts. MTOA=methyltrioctylammonium.

  连接四：配备两个会聚杯[4]吡咯单元的大三环受体具有前所未有的对两个离子对的结合特性。对于四丁基铵（TBA）盐对，观察到高度协作的结合过程。MTOA ＝甲基三辛基铵。