1,4,8,11,15,18,22,25-cctakis(hexyl)tetrabenzo[b,g,l,q][5,10,15]triazaporphinato copper | 1278592-84-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1,4,8,11,15,18,22,25-cctakis(hexyl)tetrabenzo[b,g,l,q][5,10,15]triazaporphinato copper
• 英文别名: Copper;5,8,14,17,23,26,32,35-octahexyl-2,11,20,37,39-pentaza-38,40-diazanidanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28,30(37),31,33,35-nonadecaene；copper;5,8,14,17,23,26,32,35-octahexyl-2,11,20,37,39-pentaza-38,40-diazanidanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28,30(37),31,33,35-nonadecaene
• CAS: 1278592-84-9
• 化学式: C₈₁H₁₁₃CuN₇
• 分子量: 1248.38
• InChiKey: WNWORBZYKNIPFM-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  1,4,8,11,15,18,22,25-octahexyl-29H,31H-tetrabenzo[b,g,l,q][5,10,15]triazabenzoporphyrin 在 copper diacetate 作用下， 以 戊醇 为溶剂， 反应 0.5h， 以90%的产率得到1,4,8,11,15,18,22,25-cctakis(hexyl)tetrabenzo[b,g,l,q][5,10,15]triazaporphinato copper
  参考文献：
  名称：

  酞菁类似物：意外地容易获得非外围取代的八烷基四苯并三氮杂卟啉，四苯并二氮杂卟啉，四苯并单氮杂卟啉和四苯并卟啉

  摘要：

  已经实现了酞菁/苯并卟啉杂化结构的受控合成。我们报告了一种简单的方法，该方法通过用不同量的格氏试剂处理3,6-二烷基邻苯二甲腈来获得四苯并三氮杂卟啉（TBTAP），四苯并二氮杂卟啉（TBDAP），四苯并单氮杂卟啉（TBMAP）和四苯并卟啉（TBP）大环的非周边八烷基取代衍生物甲基溴。该范围的大环产物不是通过先前报道的格氏试剂与4-取代的邻苯二甲腈的相应反应或MeMgBr与4,5-二烷基邻苯二甲腈的反应而获得的。尝试形成介观通过用苄基和长链烷基格氏试剂反应从3,6-二烷基邻苯二甲腈取代TBTAP意外得到仅在未取代的母体大环内消旋位置。到目前为止，合成协议是访问这些有趣但很少研究的材料类别的最直接，最方便的方法。以无金属以及镁和铜（II）的金属化衍生物形式获得的一系列新的取代的大环化合物，其紫外/可见光谱的趋势与小林在其他地方所预测的一致。新家族的特征允许进一步的趋势被确定为中观氮原子被次甲基

  DOI：

  10.1002/chem.201002176

文献信息

• Tetrabenzoporphyrin and -mono-, -<i>cis</i>-di- and Tetrabenzotriazaporphyrin Derivatives: Electrochemical and Spectroscopic Implications of meso CH Group Replacement with Nitrogen
  作者：Adele van As、Chris C. Joubert、Blenerhassitt E. Buitendach、Elizabeth Erasmus、Jeanet Conradie、Andrew N. Cammidge、Isabelle Chambrier、Michael J. Cook、Jannie C. Swarts

  DOI：10.1021/acs.inorgchem.5b00380

  日期：2015.6.1

  Nonperipherally hexyl-substituted metal-free tetrabenzoporphyrin (2H-TBP, 1a) tetrabenzomonoazaporphyrin (2H-TBMAP, 2a), tetrabenzo-cis-diazaporphyrin (2H-TBDAP, 3a), tetrabenzotriazaporphyrin (2H-TBTAP, 4a), and phthalocyanine (2H-Pc, 5a), as well as their copper complexes (1b-5b), were synthesized. As the number of meso nitrogen atoms increases from zero to four, lambda(max) of the Q-band absorption peak becomes red-shifted by almost 100 nm, and extinction coefficients increased at least threefold. Simultaneously the blue-shifted Soret (UV) band substantially decreased in intensity. These changes were related to the relative electron-density of each macrocycle expressed as the group electronegativity sum of all meso N and CH atom groups, Sigma chi(R). X-ray photoelectron spectroscopy differentiated between the three different types of macrocyclic nitrogen atoms (the N-inner, (NH)(inner), and N-meso) in the metal-free complexes. Binding energies of the Nmeso and Ninner,Cu atoms in copper chelates could not be resolved. Copper insertion lowered especially the cathodic redox potentials, while all four observed redox processes occurred at larger potentials as the number of meso nitrogens increased. Computational chemical methods using density functional theory confirmed 1b to exhibit a Cu(II) reduction prior to ring-based reductions, while for 2b, Cu(II) reduction is the first reductive step only if the nonperipheral substituents are hydrogen. When they are methyl groups, it is the second reduction process; when they are ethyl, propyl, or hexyl, it becomes the third reductive process. Spectro-electrochemical measurements showed redox processes were associated with a substantial change in intensity of at least two main absorbances (the Q and Soret bands) in the UV spectra of these compounds.