5,15-diphenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin | 101325-63-7

• 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-diphenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin
• 英文别名: 5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyn；ethioporphyrin；5,15-diphenyl-8,12,18,22-tetraethyl-7,13,17,23-tetramethylporphyrin；2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-diphenylporphyrin；5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin；5,15-diphenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphine；5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphine
• CAS: 101325-63-7
• 化学式: C₄₄H₄₆N₄
• 分子量: 630.876
• InChiKey: GFZCKGUWUSWNLV-OBEARYFCSA-N

物化性质

• 沸点：
  929.1±65.0 °C(Predicted)
• 密度：
  1.116±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.07
• 重原子数：
  48.0
• 可旋转键数：
  6.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  57.36
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  5,15-diphenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin 在 N-Fluoro-2,6-bis(methoxycarbonyl)pyridinium triflate 作用下， 以 氟苯 为溶剂， 生成
  参考文献：
  名称：

  meso-perfluorination of porphyrins with N-fluoropyridinium triflate

  摘要：

  Octaethylporphyrin was perfluorinated at its meso-positions with N-fluoropyridinium triflate in 67% of a total yield.

  DOI：

  10.1016/s0040-4039(00)91863-x
• 作为产物：
  描述：

  在 四氯苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以1.25%的产率得到5,15-diphenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin
  参考文献：
  名称：

  硝基取代钯和卟啉锌的结构及其光谱、配位和酸碱性质之间的相互依赖性

  摘要：

  摘要 自卟啉和相应的过渡金属配合物被用作感官、光学有用和催化活性材料的组分。目前的工作提供了使用 5,15-二苯基-2,3,7,8,12,13,17,18-八烷基卟啉的内二硝基取代衍生物与 2,3,7,8,12 进行比较的合成和分光光度实验数据,13,17,18-八乙基卟啉和 2,3,7,8,12,13,17,18-八乙基-5,15-二硝基卟啉。分析了大环变形、金属中心的性质、取代基的电子效应和介质的酸度对卟啉配位和酸碱性质的影响。结果可以得出结论，金属卟啉的形成在阴离子卟啉的情况下比在分子卟啉的情况下进行得更快，伴随着能量参数的降低。该过程伴随着能量参数的降低。在将硝基引入中间位与将硝基引入苯环的对位相反时，观察到卟啉大环的酸性质显着增加。与细观修饰相比，这种转变导致基本性质的下降可以忽略不计。与钯相比，锌和卟啉的反应进行得更快。此外，由于形成高度稳定的金属-DBU 配位络合物，最后一种

  DOI：

  10.1016/j.molstruc.2019.04.074

文献信息

• Amination of meso-bromophenyl(polyalkyl)porphyrins: Synthesis of porphyrins containing a hydroxypiperidine fragment
  作者：G. A. Artamkina、P. K. Sazonov、M. M. Shtern、G. V. Grishina、I. S. Veselov、A. S. Semeikin、S. A. Syrbu、O. I. Koifman、I. P. Beletskaya

  DOI：10.1134/s1070428008030184

  日期：2008.3

  5,15-Bis(4-bromophenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin and 5-(4-bromophenyl)-13,17-dibutyl-2,3,7,8,12,18-hexamethylporphyrin were synthesized, and their palladium-catalyzed amination with a number of cyclic secondary amines, including hydroxypiperidines, was studied [Pd(OAc)2, ligand, THF or dioxane, t-BuONa, 80–100°C]. The reactions of the meso-bromophenylporphyrins with piperidine and morpholine gave the corresponding amination products in quantitative yield. The amination with hydroxypiperidines required excess amine (3 equiv per bromine atom) and excess base (6–8 equiv) and was accompanied by formation of hydrodebromination products; in the reactions with the bis(bromophenyl)derivative, mixed products resulting from amination at one phenyl group and reductive debromination at the other were also formed. The yields of the amination products varied from good 75–50% in the reactions with 4-hydroxypiperidine and trans-3-hydroxy-4-[4-(2-fluorophenyl)piperazin-1-yl]piperidine} to moderate (20–50%, 3-hydroxypiperidine) and poor [11–25%, trans-3,4-dihydroxypiperidine and trans-3-hydroxy-4-(4-hydroxypiperidin-1-yl)piperidine].

  合成了 5,15-双（4-溴苯基）-2,8,12,18-四乙基-3,7,13,17-四甲基卟啉和 5-（4-溴苯基）-13,17-二丁基-2,3,7,8,12,18-六甲基卟啉、并研究了它们与一些环状仲胺（包括羟基哌啶）的钯催化胺化反应[Pd(OAc)2，配体，THF 或二氧六环，t-BuONa，80-100°C]。中溴代苯基卟啉与哌啶和吗啉的反应得到了相应的胺化产物，且产率很高。与羟基哌啶的胺化反应需要过量的胺（每个溴原子 3 个等量物）和过量的碱（6-8 个等量物），并伴随着氢脱溴产物的形成；在与双（溴苯基）衍生物的反应中，还形成了由一个苯基上的胺化反应和另一个苯基上的还原脱溴反应产生的混合产物。胺化产物的收率有高有低在与 4-羟基哌啶和反式-3-羟基-4-[4-(2-氟苯基)哌嗪-1-基]哌啶的反应中为 75-50%}，也有中等收率（20-50%，3-羟基哌啶）和低收率（11-25%，反式-3,4-二羟基哌啶和反式-3-羟基-4-(4-羟基哌啶-1-基)哌啶）。
• A novel approach to the synthesis of symmetrical and unsymmetrical porphyrin dimers
  作者：Ravindra K. Pandey、Timothy P. Forsyth、Kevin R. Gerzevske、Jack J. Lin、Kevin M. Smith

  DOI：10.1016/s0040-4039(00)79081-2

  日期：1992.9

  Methodology for synthesis of symmetrical or unsymmetrical porphyrin dimers linked at the meso positions with phenyl or stilbene functionalities is reported; 5-porphyrinyl-dipyrromethanes are key intermediates in this approach.

  报道了在内消旋位置与苯基或二苯乙烯官能团连接的对称或不对称卟啉二聚体的合成方法；5-卟啉基-二吡咯甲烷是该方法中的关键中间体。
• Synthesis and coordination properties of nitro derivatives of 5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin
  作者：E. M. Kuvshinova、I. A. Vershinina、S. A. Syrbu、O. A. Golubchikov

  DOI：10.1134/s1070363217090444

  日期：2017.9

  the synthesis of nitro derivatives of 5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin containing nitro groups at the meso positions of the porphyrin core and at the para positions of the phenyl substituents. The formation kinetics of the zinc, copper, and cobalt complexes of the resultant porphyrins in pyridine and in an acetic acid–benzene (7 : 3) mixed solvent was studied. It was

  开发了合成5,15-二苯基-3,7,13,17-四甲基-2,8,12,18-四乙基卟啉的硝基衍生物的方法，在卟啉核心的介孔位置和对位苯基取代基的位置。研究了所得卟啉在吡啶和乙酸-苯（7：3）混合溶剂中锌，铜和钴配合物的形成动力学。已经发现，卟啉配体的性质既取决于硝基的电子效应，又取决于卟啉核心的空间变形的效应。
• ——
  作者：S. A. Syrbu、T. V. Lyubimova、A. S. Semeikin

  DOI：10.1023/a:1013936027631

  日期：——

  The electronic and steric effects of peripheral substituents on the yield of 5,15-diphenyloctaalkylporphines were studied. It was found that the electronic nature of substituents in the starting benzaldehydes exerts almost no yield effect. At the same time, there is some optimal size of substituents, which provides the highest possible yield of porphyrins.
• Aryl Ring Rotation in Porphyrins. A Carbon-13 NMR Spin−Lattice Relaxation Time Study
  作者：Lori Noss、Paul A. Liddell、Ana L. Moore、Thomas A. Moore、Devens Gust

  DOI：10.1021/jp962209y

  日期：1997.1.1

  Overall tumbling and internal rotational motions in porphyrins bearing meso aryl substituents and, in some cases, flanking alkyl groups at the beta-pyrrolic positions have been determined using C-13 spin-lattice relaxation time measurements. In deuteriochloroform solution at 303 K, the overall reorientation of all three porphyrins investigated occurs with diffusion coefficients of similar to 1 x 10(9) s(-1). In porphyrins with only hydrogen at the beta-pyrrolic positions, the meso phenyl rings undergo rotations about their single bonds to the porphyrin with diffusion coefficients of similar to 4 x 10(9) s(-1). Introduction of methyl substituents at the beta-pyrrolic positions adjacent to the phenyl rings reduces these motions, but only to similar to 1 x 10(9) s(-1). Thus, significant internal motions are present in both types of molecules. These motions occur on the time scale of many photoinduced electron and energy transfer processes in porphyrins covalently linked to electron or energy donors or accepters through meso aryl groups. Thus, the internal librational motions may affect rates of photoinduced electron and energy transfer, even in relatively ''rigid'' molecular constructs.