10,20-dimesityl-5,15-diazaporphyrin | 1409954-68-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 10,20-dimesityl-5,15-diazaporphyrin
• 英文别名: 7,17-Bis(2,4,6-trimethylphenyl)-2,12,21,22,23,24-hexazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(21),2,4,6,8,10,12,14,16(22),17,19-undecaene；7,17-bis(2,4,6-trimethylphenyl)-2,12,21,22,23,24-hexazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(21),2,4,6,8,10,12,14,16(22),17,19-undecaene
• CAS: 1409954-68-2
• 化学式: C₃₆H₃₂N₆
• 分子量: 548.69
• InChiKey: PCVXDZIACXDMSL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  42
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  83.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  10,20-dimesityl-5,15-diazaporphyrin 在 gold(III) chloride 、 N-溴代丁二酰亚胺(NBS) 、 silver trifluoromethanesulfonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 以41%的产率得到4-Bromo-7,17-bis(2,4,6-trimethylphenyl)-2,12,21,22,23,24-hexazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1,3,5,7,9,11,13(22),14,16,18(21),19-undecaene
  参考文献：
  名称：

  Site-selective halogenation on meso-mesityl substituents of 10,20-dimesityl-5,15-diazaporphyrins with an AuX₃/AgOTf combination

  摘要：

  一种AuBr₃/AgOTf组合物实现了对10,20-二间苯基-5,15-二氮杂卟啉中间体上间苯基取代基的位选择性溴化。

  DOI：

  10.1039/d0dt02727h

文献信息

• Manganese(III) 5,15-diazaporphyrins: Synthesis, properties, and catalytic use for benzylic C–H fluorination
  作者：Shiho Mori、Tsubasa Nishimura、Hiroshi Shinokubo、Yoshihiro Miyake

  DOI：10.1142/s1088424621500887

  日期：2021.10

  promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp3 C–H bonds. Recently, we have found that iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp2-hybridized nitrogen atoms at the meso-positions, showed high catalytic performance in the oxidation of sp3 C–H bonds

  sp 3 C-H键的氟化作为一种​​有前途的有机氟化合物合成方法引起了相当大的关注。锰卟啉作为催化剂在饱和 sp 3 C-H 键的氟化中得到了广泛的研究。最近，我们发现铁(III) 5,15-二氮杂卟啉是一种卟啉类似物，具有亚胺型 sp 2杂化氮原子。中观-位置，在sp 3 C-H键的氧化中显示出高催化性能。在这里，我们公开了锰 (III) 5,15-二氮杂卟啉的合成、结构和电子特性。我们还展示了氯锰 (III) 5,15-二氮杂卟啉对苄基氟化的催化作用。
• Iron(III) 5,15-Diazaporphyrin Catalysts for the Direct Oxidation of C(sp³)–H Bonds
  作者：Tsubasa Nishimura、Takahisa Ikeue、Osami Shoji、Hiroshi Shinokubo、Yoshihiro Miyake

  DOI：10.1021/acs.inorgchem.0c02166

  日期：2020.11.2

  also demonstrate that chloroiron(III) 5,15-diazaporphyrins exhibit high catalytic activity in the direct oxidation of alkanes due to their intrinsic electron-deficient nature. On the basis of stoichiometric reactions of iron(III) diazaporphyrin with iodosylbenzene as an oxidant, it was possible to demonstrate the existence of an iodosylbenzene–iron diazaporphyrin adduct reaction intermediate that serves

  5,15- Diazaporphyrins是卟啉与亚胺型SP类似物2个的杂化的氮原子的内消旋-位置。即使这些化合物比常规卟啉更缺乏电子，但尚未报道使用二氮杂卟啉铁作为催化剂。在这里，我们公开了铁（III）5,15-二氮杂卟啉的合成，结构和电子性质。我们通过X射线分析和电化学分析评估其结构和电子性质。我们还证明，由于其固有的电子缺陷性质，氯铁（III）5,15-二氮杂卟啉在烷烃的直接氧化中表现出高催化活性。根据铁（III）二氮杂卟啉与碘基苯作为氧化剂的化学计量反应，有可能证明存在碘基苯-铁二氮杂卟啉加合物反应中间体，该中间体可作为生成氧代铁物种的储库。
• Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids
  作者：Ayaka Yamaji、Hayato Tsurugi、Yoshihiro Miyake、Kazushi Mashima、Hiroshi Shinokubo

  DOI：10.1002/chem.201600066

  日期：2016.3.14

  Reagent‐controlled chemo‐ and regioselective reduction of 5,15‐diazaporphyrins has been developed. The selective reduction of carbon–carbon double bonds of diazaporphyrins provides 18 π aromatic isobacteriochlorin‐type products, whereas the reduction of carbon–nitrogen double bonds leads to selective formation of 20 π N,N′‐dihydrodiazaporphyrins in excellent yields. The distinct antiaromatic character

  已经开发了通过试剂控制的5,15-二氮杂卟啉的化学和区域选择性还原反应。的diazaporphyrins的碳-碳双键的选择性还原提供18π芳香族isobacteriochlorin型产品，而碳-氮双键的引线的还原到π20的选择性形成Ñ，Ñ以优良产率'-dihydrodiazaporphyrins。N，N′-二氢二氮杂卟啉具有独特的抗芳香特性。与相应的18π卟啉相比，游离碱N，N'-二氢二氮杂卟啉显示出更慢的内部NH互变异构现象。
• Synthesis and Photovoltaic Properties of Phenylethynyl-substituted Diazaporphyrin
  作者：Kei Kurotobi、Kyosuke Kawamoto、Yuuki Toude、Yamato Fujimori、Yuriko Kinjo、Seigo Ito、Yoshihiro Matano、Hiroshi Imahori

  DOI：10.1246/cl.130212

  日期：2013.7.5

  Carboxyphenylethynyl-substituted diazaporphyrin has been synthesized to assess the utility of diazaporphyrins in dye-sensitized solar cells for the first time. The diazaporphyrin-sensitized TiO2 cell exhibited photocurrent generation in the visible region of 400–700 nm together with a power conversion efficiency of 0.08%.

  为了评估重氮卟啉在染料敏化太阳能电池中的用途，我们首次合成了羧基苯乙炔基取代的重氮卟啉。重氮卟啉敏化二氧化钛电池在波长为 400-700 纳米的可见光区产生光电流，功率转换效率为 0.08%。
• Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers
  作者：Satoshi Omomo、Takuma Sugai、Mao Minoura、Haruyuki Nakano、Yoshihiro Matano

  DOI：10.1002/anie.201800471

  日期：2018.3.26

  for the base‐promoted direct amination of β‐unsubstituted 5,15‐diazaporphyrins (DAPs) with secondary and primary amines to produce 3,7,13,17‐tetraamino‐ and 3‐amino‐DAPs, respectively, regioselectively. The amino groups attached at the periphery cause significant red shifts of the absorption bands as a result of their perturbation of the HOMO and/or LUMO in the DAP π‐system. The palladium complex of a

  我们已经建立了一种方便的方法，用于用仲胺和伯胺对β-未取代的5,15-二氮杂卟啉（DAP）进行碱促进的直接胺化，以分别生成3,7,13,17-四氨基-和3-氨基-DAP ，区域选择性地。由于在DAPπ系统中对HOMO和/或LUMO的扰动，连接在外围的氨基导致吸收带发生明显的红移。3,7,13,17-四（二苯基氨基）-DAP的钯配合物在近红外光照射下高产产生单线态氧。