[meso-tetraphenyl-2,3-vic-diolchlorinato]nickel(II) | 203568-12-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [meso-tetraphenyl-2,3-vic-diolchlorinato]nickel(II)
• 英文别名: meso-tetraphenyl-2,3-dihydroxychlorinatonickel(II)；Ni(Ph4C20H8N4(OH)2)
• CAS: 203568-12-1
• 化学式: C₄₄H₃₀N₄NiO₂
• 分子量: 705.438
• InChiKey: CIQKHVRASAFMSP-BFSAKQSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.18
• 重原子数：
  51.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  94.44
• 氢给体数：
  2.0
• 氢受体数：
  4.0

文献信息

• <i>meso</i>-Arylporpholactones and their Reduction Products
  作者：Christian Brückner、Junichi Ogikubo、Jason R. McCarthy、Joshua Akhigbe、Michael A. Hyland、Pedro Daddario、Jill L. Worlinsky、Matthias Zeller、James T. Engle、Christopher J. Ziegler、Matthew J. Ranaghan、Megan N. Sandberg、Robert R. Birge

  DOI：10.1021/jo300963m

  日期：2012.8.3

  chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2-oxachlorin (11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles

  详细介绍了内消旋四芳基-3-氧代-2-氧杂卟啉5（称为卟啉内酯）的合理合成，通过 MnO 4 –介导的相应内消旋四芳基-2,3-二羟基二氢卟酚 ( 7 ) 的氧化作用进行了详细说明。由于二氢卟酚7是由母体卟啉1制备的，这相当于用恶唑酮部分对1中的吡咯部分进行 2 步置换。卟啉内酯5的逐步还原导致形成二氢卟酚类似物、内消旋-tetraaryl-3-hydroxy-2-oxachlorin ( 11 ) 和内消旋四芳基-2-oxachlorin (12 )。描述了11与 O-、N-和 S-亲核试剂亲核取代的反应性。用恶唑酮（类卟啉发色团）或（取代的）恶唑部分（二氢卟酚类发色团，对于母体恶唑并绿素12，红移 Q x）正式取代吡咯的深刻光物理后果具有增强的振荡器强度的波段）在 SAC-CI 和 MNDO-PSDCI 分子轨道理论计算的基础上进行了详细和合理化。卟啉内酯的单晶 X 射线结构指向羰基氧
• Synthesis of indaphyrins: meso-tetraarylsecochlorin-based porphyrinoids containing direct o-phenyl-to-β-linkages
  作者：Jason R. McCarthy、Michael A. Hyland、Christian Brückner

  DOI：10.1039/b401629g

  日期：——

  The synthesis of indaphyrins, novel meso-tetraarylsecochlorin-derived chromophores incorporating o-phenyl-to-β-linkages, is described. Oxidative diol cleavage of meso-tetraaryl-2,3-dihydroxy-2,3-chlorins results in the formation of a secochlorin bisaldehyde. Depending on the reaction conditions during the ring cleavage reaction, one or two of the aldehyde groups react with the adjacent o-phenyl positions, leading to an intramolecular electrophilic aromatic substitution of the o-phenyl proton, and the establishment of a direct o-phenyl-to-β-linkage. The initially formed carbinol is spontaneously oxidized to the corresponding ketone. This modification forces the aryl groups into co-planarity with the macrocycle, allowing for interactions between the π-electrons of the aryl groups, the ketone linkage, and those of the chromophore, resulting in a significant electronic modulation of the porphyrinic π-system. The UV-vis spectroscopic properties of the free base, CuII, NiII, and ZnII indaphyrins are discussed.

  本研究描述了吲达霉素的合成过程，吲达霉素是一种新型中-四芳基-secochlorin 衍生的发色团，含有邻苯基-δ-连接。中-四芳基-2,3-二羟基-2,3-氯素的氧化二醇裂解会形成仲氯素双醛。根据裂环反应过程中的反应条件，一个或两个醛基会与邻近的邻苯基位置发生反应，导致邻苯基质子发生分子内亲电芳香取代反应，并建立邻苯基与δ的直接连接。最初生成的甲醇会自发氧化成相应的酮。这种修饰迫使芳基与大环共面，使芳基的Ï电子、酮连接和发色团的Ï电子之间发生相互作用，从而对卟啉Ï系统产生显著的电子调节作用。本文讨论了游离碱、CuII、NiII 和 ZnII indaphyrins 的紫外-可见光谱特性。
• Helimeric Porphyrinoids: Stereostructure and Chiral Resolution of <i>meso</i>-Tetraarylmorpholinochlorins
  作者：Christian Brückner、Daniel C. G. Götz、Simon P. Fox、Claudia Ryppa、Jason R. McCarthy、Torsten Bruhn、Joshua Akhigbe、Subhadeep Banerjee、Pedro Daddario、Heather W. Daniell、Matthias Zeller、Ross W. Boyle、Gerhard Bringmann

  DOI：10.1021/ja202451t

  日期：2011.6.8

  and the dialkoxy derivatives. The Ni(II) complexes were all found to be severely ruffled whereas the free-base chromophores are more planar. As a result of the helimeric distortion of their porphyrinoid chromophores, the ruffled macrocycles possess a stable inherent element of chirality. Most significantly, resolution of the racemic mixtures was achieved, both by classical methods via diastereomers

  描述了游离碱和 Ni(II) 配合物的许多衍生物的合成和手性拆分，其中有和没有与侧翼苯基的直接 β-碳-邻-苯基连接。吗啉二氢卟酚是一类稳定的二氢卟酚类似物，是由内消旋四苯基卟啉分两到三步合成的。这些吗啉二氢化合物的各种游离碱和 Ni(II) 配合物的构象和相对立体结构通过 X 射线衍射进行了阐明。立体和立体电子论点解释了吗啉取代基的相对立体排列，它们在游离碱和 Ni(II) 配合物、单烷氧基、β-碳-邻-苯基连接的吗啉二氢卟吩和二烷氧基衍生物中有所不同。Ni(II) 配合物都被发现有严重的褶皱，而游离碱发色团则更平坦。由于其类卟啉发色团的螺旋体畸变，褶皱大环具有稳定的固有手性元素。最重要的是，通过非对映异构体的经典方法和手性相上的 HPLC 实现了外消旋混合物的拆分。使用量子化学计算方法记录和建模完整的 CD 光谱，首次允许分配生色团的绝对构型。该报告扩展了已知的吡咯改性卟啉的范围。除此之外，它还引入了大型手性卟啉
• Microwave-promoted insertion of Group 10 metals into free base porphyrins and chlorins: scope and limitations
  作者：Michelle L. Dean、Jason R. Schmink、Nicholas E. Leadbeater、Christian Brückner

  DOI：10.1039/b716181f

  日期：——

  The scope and limitations of microwave heating as a tool for insertion of Group 10 metals into meso-tetraphenyl-porphyrin, -porpholactone, and -2,3-dihydroxychlorin derivatives are discussed. In some cases it is possible to reduce reaction times dramatically while obtaining good yields of the metallated products while in others new issues arise relating to the metal salt used as well as acceleration not only of the metallation reaction but also of byproduct formation.

  本文讨论了微波加热作为将第 10 族金属加入中四苯基卟啉、卟啉内酯和-2,3-二羟基氯素衍生物的工具的范围和局限性。在某些情况下，可以显著缩短反应时间，同时获得较高的金属化产物产率；而在另一些情况下，则会出现与所使用的金属盐有关的新问题，不仅会加速金属化反应，还会加速副产品的形成。
• Pyrazinoporphyrins: Expanding a Pyrrolic Building Block in <i>meso</i> -Tetraphenylporphyrin by a Nitrogen Atom
  作者：Michelle L. Head、Gloria Zarate、Christian Brückner

  DOI：10.1002/ejoc.201501436

  日期：2016.2

  the resulting seco-chlorin bis(aldehyde) with ammonia – generates pyrazinoporphyrins. Thus, a nitrogen atom was inserted between the two former β-carbon atoms, overall formally replacing a pyrrolic building block by a pyrazine moiety. Treatment of the initially formed pyrazine hemiaminals with alcohols converts them into the corresponding hemiaminal ethers. This stabilizes the chromophores significantly

  将我们的“卟啉破坏和修复策略”的变体应用于内消旋四芳基卟啉的游离碱和 NiIII 复合物——二羟基化、氧化二醇裂解以及所得二氢二氢卟酚双（醛）与氨的反应——生成吡嗪卟啉。因此，一个氮原子被插入到两个之前的 β-碳原子之间，总体上用吡嗪部分正式取代了吡咯结构单元。用醇处理最初形成的吡嗪半缩醛，将它们转化为相应的半缩醛醚。这显着地稳定了发色团，但游离碱吡嗪卟啉仍然对（酸诱导的）降解反应保持敏感。游离碱吡嗪卟啉具有略微红移的卟啉型 UV/Vis 光谱，