5,10,15,20-tetrakisphenyl-21,23-dithiaporphyrin | 57511-57-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 5,10,15,20-tetrakisphenyl-21,23-dithiaporphyrin
• 英文别名: 5,10,15,20-Tetrakis-phenyl-21,23-ditiaporphyrin；5,10,15,20-tetraphenyl-21,23-dithiaporphyrin；meso-tetraphenyl-21,23-dithiaporphyrin；21,23-dithiatetraphenylporphyrin；S2TPP；2,4,6,8-tetraphenyl-1,5(2,5)-dipyrrola-3,7(2,5)-dithiophena-cyclooctaphane-1(2),4,6,7(8)-tetraene
• CAS: 57511-57-6
• 化学式: C₄₄H₂₈N₂S₂
• 分子量: 648.852
• InChiKey: NAHFWYVLDQUWFI-RKKMNUGNSA-N

物化性质

• 熔点：
  >300 °C
• 密度：
  1.265±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.79
• 重原子数：
  48.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.78
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  5,10,15,20-tetrakisphenyl-21,23-dithiaporphyrin 在 高氯酸 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Physicochemical Basis for the Creation of Liquid-Phase Sensor Materials Based on Tetraaryldithiaporphyrins

  摘要：

  DOI：

  10.1134/s1070363222020128
• 作为产物：
  描述：

  苯甲醛 、 alkaline earth salt of/the/ methylsulfuric acid 在 正丁基锂 、 四甲基乙二胺 、 乙酸酐 、 丙酸 作用下， 以 正己烷 为溶剂， 反应 2.0h， 生成 5,10,15,20-tetrakisphenyl-21,23-dithiaporphyrin
  参考文献：
  名称：

  Water-Soluble, Core-Modified Porphyrins as Novel, Longer-Wavelength-Absorbing Sensitizers for Photodynamic Therapy

  摘要：

  Water-soluble, core-modified 5,10,15,20-tetrakis(4-sulfonatophenyl)-21,23-dithiaporphyrin (1) and 5,10,15,20-tetrakis(4-sulfonatophenyl)-21,23-diselenaporphyrin (2) were prepared as the tetrasodium salts by the sulfonation of 5,10,15,20-tetraphenyl-21,23-dithiaporphyrin (3) and -21,23-diselenaporphyrin (4), respectively, with sulfuric acid. Compounds 3 and 4 were prepared by the condensation of pyrrole with either 2,5-bis(phenylhydroxymethyl)thiophene (5) or 2,5-bis(phenylhydroxymethyl)selenophene (6) in propionic acid. The addition of benzaldehyde to 2,5-dilithiothiophene or 2,5-dilithioselenophene gives 5 or 6, respectively, as a nearly equimolar mixture of meso- and d,l-diastereomers. Careful crystallization of 5 gives a single diastereomer by removing the crystalline product from the equilibrating mixture of diastereomers in solution, Photodynamic therapy (PDT) with 1 has an LD50 of less than 25 mu g/mL against Colo-26 cells in culture and exhibits a lethal dose for 90% or more at concentrations greater than 50 mu g/mL. In contrast, PDT with 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) requires concentrations of greater than 100 mu g/mL to achieve LD50 Neither 1 nor TPPS4 shows significant photoactivity against the murine T-cell line, MOLT-4, above the dark toxicity. Sensitizer 1 shows no toxicity or side effects in BALB/c mice observed for 30 days following a single intravenous injection of 10 mg (9.1 mu mol)/kg. Distribution studies show that sensitizer 1 accumulates in the tumors of BALB/c mice bearing Cole-26 or EMT-6 tumors with sensitizer concentration roughly doubling as the dosage of 1 increased from 5 to 10 mg/kg. In vivo studies show that PDT with sensitizer 1 at both 3.25 and 10 mg/kg with 135 cm(-2) of 694-nm light is effective against Cola-26 tumors in BALB/c mice.

  DOI：

  10.1021/jm000044i

文献信息

• Synthesis of β-Substituted<i>meso</i>-Tetraaryl-21,23-dithiaporphyrins by Heck Reaction
  作者：Luana da S. M. Forezi、Ana T. P. C. Gomes、Maria G. P. M. S. Neves、Vitor F. Ferreira、Fernanda da C. S. Boechat、Maria C. B. V. de Souza、José A. S. Cavaleiro

  DOI：10.1002/ejoc.201500812

  日期：2015.9

  meso-Tetraphenyl-21,23-dithiaporphyrin was selectively monobrominated at one β-pyrrolic position in good yields. This dithiaporphyrin was then functionalized by Heck reaction with styrene derivatives containing different electronic features. The reaction profile was found to depend on the electronic characteristics of the styrene derivatives; the new compounds were fully characterized.

  meso-Tetraphenyl-21,23-dithiaporphyrin 在一个 β-吡咯位置被选择性地单溴化，产率很高。然后通过与含有不同电子特征的苯乙烯衍生物的 Heck 反应将这种二硫卟啉官能化。发现反应曲线取决于苯乙烯衍生物的电子特性；对新化合物进行了充分表征。
• Facile Redox‐Induced Aromatic–Antiaromatic Interconversion of a β‐Tetracyano‐21,23‐Dithiaporphyrin under Ambient Conditions
  作者：Ken‐ichi Yamashita、Kana Nakajima、Yusuke Honda、Takuji Ogawa

  DOI：10.1002/chem.201905823

  日期：2020.3.18

  aromatic-antiaromatic interconversions were accomplished by using β-tetracyano-21,23-dithiaporphyrin (CN4 S2 Por). Introduced cyano groups not only increased the reduction potential of the porphyrin core but also stabilized the antiaromatic isophlorin (CN4 S2 Iph) by π conjugation. The reduction of CN4 S2 Por with hydrazine in polar solvents quantitatively affords CN4 S2 Iph, even under ambient conditions. CN4 S2

  通过使用β-四氰基21,23-二硫杂卟啉（CN4 S2 Por），可以轻松实现氧化还原诱导的芳族-抗芳族相互转化。引入的氰基基团不仅增加了卟啉核心的还原电位，而且还通过π结合稳定了抗芳香族异佛洛林（ S2 Iph）。即使在环境条件下，在极性溶剂中用肼还原 S2 Por仍可定量提供 S2 Iph。 S2Iph保留几乎平面的构象并表现出相当大的抗芳香性。 S2 Iph有氧氧化为 S2 Por在非极性溶剂中发生。进行该研究有助于理解结构-抗芳香性关系。
• Novel Core-Modified Expanded Porphyrins with <i>meso</i>-Aryl Substituents:  Synthesis, Spectral and Structural Characterization
  作者：Seenichamy Jeyaprakash Narayanan、Bashyam Sridevi、Tavarekere K. Chandrashekar、Ashwani Vij、Raja Roy

  DOI：10.1021/ja991472k

  日期：1999.10.1

  spectral and structural characterization of meso-aryl sapphyrins and rubyrins containing heteroatoms such as S, O, Se in addition to pyrrole nitrogens are reported. The synthesis of the desired expanded porphyrins has been achieved using a single precursor, the modified tripyrranes containing heteroatoms, through an unprecedented oxidative coupling reaction in moderately good yields. The product distribution

  报道了除吡咯氮外还含有 S、O、Se 等杂原子的内消旋芳基蓝宝石和红宝石的合成、光谱和结构表征。使用单一前体，即含有杂原子的改性三吡喃，通过前所未有的氧化偶联反应以中等良好的产率合成了所需的膨胀卟啉。发现产物分布和分离的产率取决于酸催化剂的性质及其浓度。使用 0.1 当量的酸仅产生 26π 红宝石，而较高浓度的酸产生 18π 卟啉、22π 蓝宝石和 26π 红宝石的混合物。在 oxatripyrrane 的反应中分离出另外两种产物 22π oxasmaragdyrin 和 18π oxacorrole。
• meso-Aryl sapphyrins with heteroatoms; synthesis, characterization, spectral and electrochemical properties
  作者：Alagar Srinivasan、Simi K. Pushpan、Murugaeson Ravi Kumar、Sumeet Mahajan、Tavarekere K. Chandrashekar、Raja Roy、P. Ramamurthy

  DOI：10.1039/a900137i

  日期：——

  The synthesis, characterization and spectral properties of six new meso-aryl core modified sapphyrins are described. An efficient approach involving an acid catalyzed condensation of bithiophene diol 1 and modified tripyrranes 2a–2e allows preparation of the desired meso-aryl sapphyrins in 16–36% yield. The product distribution and the isolated yield were found to be dependent on the nature of the acid catalyst (Lewis acid or protic acid) and its concentration. Protic acid catalyst exclusively gave the expected sapphyrins while two additional products, an 18π tetraphenylporphyrin and a 26π modified rubyrin, were isolated under Lewis acid catalysis. An analysis of proton NMR and absorption spectral data suggests that in free base sapphyrins, the heterocyclic ring opposite to the bithiophene unit is inverted as in N-5 meso-aryl sapphyrin and the degree of inversion is dependent on the nature of the heterocyclic ring. The energy optimized structure calculated from the semi-empirical method substantiates such a conclusion. Protonation of sapphyrins generates respective mono- and dications and the heterocyclic ring retains an inverted structure in contrast to normal N-5 sapphyrins. The triplet excited lifetimes for free base and protonated derivatives are similar both under argon saturated and air equilibrated conditions, indicating that the triplet state quenching by oxygen is minimal. Cyclic voltammetric studies reveal easier reductions and harder oxidations relative to meso-aryl porphyrins and the Δredox observed for 3d suggests significant reduction of the HOMO–LUMO energy gap consistent with the large red shift observed for the Soret band.

  描述了六种新的meso-芳基核心改性萨非林的合成、表征和光谱特性。采用一种高效的方法，通过酸催化的双噻烯二醇1和改性三吡咯烷2a-2e的凝缩反应，可以在16-36%的产率下制备所需的meso-芳基萨非林。产物分布和分离产率依赖于酸催化剂的性质（路易斯酸或质子酸）及其浓度。质子酸催化剂仅产生预期的萨非林，而在路易斯酸催化下则分离出两种额外产物，分别为18π四苯基卟啉和26π改性红色素。对质子NMR和吸收光谱数据的分析表明，在自由碱萨非林中，与双噻烯单元相对的杂环环结构颠倒，类似于N-5 meso-芳基萨非林，而颠倒的程度依赖于杂环的性质。从半经验方法计算得到的能量优化结构证实了这一结论。萨非林的质子化生成相应的单阳离子和双阳离子，而杂环结构保持颠倒，与正常的N-5萨非林形成对比。在氩气饱和和空气平衡条件下，自由碱和质子化衍生物的三重激发寿命相似，表明氧对三重态的淬灭作用很小。循环伏安研究显示，相对于meso-芳基卟啉，萨非林易于还原而难以氧化，3d中观察到的Δ红ox表明HOMO-LUMO能隙显著减少，与Soret带观察到的红移相一致。
• cis-Pyridyl core-modified porphyrins for the synthesis of cationic water-soluble porphyrins and unsymmetrical non-covalent porphyrin arrays
  作者：Sangita Santra、Duraisamy Kumaresan、Neeraj Agarwal、Mangalampalli Ravikanth

  DOI：10.1016/s0040-4020(03)00183-2

  日期：2003.3

  Synthesis of a series of 21-thia and 21-oxoporphyrin building blocks containing two pyridyl functional groups at the meso positions in a cis fashion is reported. The building blocks were used to synthesize a series of cationic water-soluble 21-thia and 21-oxoporphyrins. An unsymmetrical non-covalent trimer containing two dissimilar porphyrin cores such as one N3S and two N4 porphyrins cores was also

  据报道，以顺式方式合成了在内消旋位置含有两个吡啶基官能团的一系列21-硫杂和21-氧卟啉结构单元。这些构建基块用于合成一系列阳离子水溶性21-硫杂和21-氧卟啉。还使用此处报道的吡啶基卟啉结构单元构建了包含两个不同的卟啉核心（例如一个N 3 S和两个N 4卟啉核心）的不对称非共价三聚体。