5-(4-羧基甲基苯基)-10,15,20-三(4-甲基苯基)卟啉 | 57105-80-3

• 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
• 中文名称: 5-(4-羧基甲基苯基)-10,15,20-三(4-甲基苯基)卟啉
• 英文名称: 5-(4-methoxycarbonylphenyl)-10,15,20-tri-p-tolylporphyrin
• CAS: 57105-80-3
• 化学式: C₄₉H₃₈N₄O₂
• 分子量: 714.866
• InChiKey: HHCWSNARTNIMDE-PJEPRTEXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.04
• 重原子数：
  55.0
• 可旋转键数：
  5.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  83.66
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  5-(4-羧基甲基苯基)-10,15,20-三(4-甲基苯基)卟啉 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以84%的产率得到5-(4-hydroxymethylphenyl)-10,15,20-tris(4-methylphenyl)porphyrin
  参考文献：
  名称：

  基于卟啉-四极的三联体协同双光子诱导荧光和单线态氧产生

  摘要：

  结合芴核双供体四极染料的大双光子吸收特性和卟啉亚基的显着敏化特性（即高系统间交叉和通过能量产生单线态氧的能力）的协同多发色三联体系统的设计和合成描述了从其三重激发态向氧的转移）。辐照后，能量可以通过 FRET 过程以 80% 的效率从四极发色团转移到卟啉。此外，四极亚基的双光子吸收特性和卟啉的敏化和荧光特性都得到了保留，这表明由于实施的设计，在这种分子结构中可以防止有害的竞争过程（例如光诱导电子转移）。结果发现，与卟啉亚基相比，近红外区域三联体的双光子吸收诱导单线态氧生成效率提高了一个数量级。这些基于卟啉的多发色系统在近红外区域基于双光子激发的光动力治疗中的潜在应用可能是可能的，因为它克服了卟啉的低双光子吸收响应，同时完全保留了它们显着的光敏特性。发现与卟啉亚基相比，近红外区域三联体的双光子吸收诱导的单线态氧生成效率提高了一个数量级。这些基于卟啉的多发色系统在近红外区域基于双光子激发的光动

  DOI：

  10.1142/s1088424616501248
• 作为产物：
  描述：

  1,9-双(4-甲基苯甲酰基)-5-(4-甲基苯基)二吡咯甲烷 在 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 生成 5-(4-羧基甲基苯基)-10,15,20-三(4-甲基苯基)卟啉
  参考文献：
  名称：

  Porphyrin Architectures Tailored for Studies of Molecular Information Storage

  摘要：

  A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Zinc porphyrins tethered to Au(111) or Si(100) provide a benchmark for studies of information storage. Three sets of porphyrins have been synthesized for studies of the interplay of molecular design and charge-storage properties: (1) A set of porphyrins is described for probing the effect of surface attachment atom on electron-transfer kinetics. Each porphyrin bears a meso-CH2X group for surface attachment where X = OH, SAc, or SeAc. (2) A set of porphyrins is described for studying the effect of surface-charge density in monolayers. Each porphyrin bears a benzyl alcohol for surface attachment and three nonlinking meso substituents of a controlled degree of bulkiness. (3) A set of porphyrins is described that enables investigation of on-chip patterning of the electrolyte. Each porphyrin bears a formyl group distal to the surface attachment group for subsequent derivatization with a molecular entity that comprises the electrolyte. Taken together, this collection of molecules enables a variety of studies to elucidate design issues in molecular-based information storage.

  DOI：

  10.1021/jo0498260

文献信息

• Synthesis of a beta-turn forming depsipeptide for hydrogen bond mediated electron transfer studies
  作者：David A. Williamson、Bruce E. Bowler

  DOI：10.1016/0040-4020(96)00743-0

  日期：1996.9

  Hydrogen bonds are believed to play an important role in the mediation of electron transfer processes in proteins. A porphyrin/depsipeptide/p-benzoquinone molecule has been synthesized to help understand this role of hydrogen bond mediated electron transfer in proteins. The synthesis, room temperature folding conformation, and steady-state electron transfer are described.

  据信氢键在蛋白质中电子转移过程的介导中起重要作用。已经合成了卟啉/二肽/对苯醌分子，以帮助理解蛋白质中氢键介导的电子转移的这种作用。描述了合成，室温折叠构象和稳态电子转移。
• Synthesis of porphyrin dyads with potential use in solar energy conversion
  作者：Fernando Fungo、Luis A. Otero、Leonides Sereno、Juana J. Silber、Edgardo N. Durantini

  DOI：10.1039/a907428g

  日期：——

  A convenient procedure for the synthesis of porphyrin derivative dyads is described. The dyads consist of a free base porphyrin covalently linked to a zinc porphyrin or ferrocene by an amide bond. 5-(4-Substituted phenyl)-10,15,20-tris(4-methylphenyl) porphyrins were synthesized from meso-(4-methylphenyl) dipyrromethanes 1, which was obtained with appreciable yield (83%). The reaction of dipyrromethane 1 with a mixture of two appropriate substituted benzaldehydes affords the desired meso-substituted porphyrins, which can be easily separated by flash chromatography. These porphyrins bearing either one 4-acetamidophenyl group 2 or 4-carboxymethylphenyl group 3, and three 4-methylphenyl peripheral functional groups, were prepared with notable yields (15–17%) in a two-step one-flask reaction. Basic hydrolysis of the porphyrins 2 and 3 yielded amino 4 and acid porphyrin 5, respectively. Treatment of 5 with zinc acetate afforded the corresponding metal complex Zn-acid porphyrin 6. The dyads 7 and 8 were obtained by the coupling reaction between the acid chloride derivatives of either Zn-acid porphyrin 6 or ferroceneacetic acid and amino porphyrins 4, respectively. The present strategy may be easily used for preparation of other similar dyad derivatives. These compounds could have interesting applications in electronic materials. Preliminary studies of light energy conversion by SnO2 electrodes coated with porphyrin dyads 7 and 8 were performed. The results show that dyads 7 and 8 may be suitable for solar energy conversion devices.

  描述了一种合成卟啉衍生物二聚体的方便程序。该二聚体由一个自由基卟啉通过酰胺键与锌卟啉或铁烯连接。通过从中间体（4-甲基苯基）二吡咯烷1中合成出5-(4-取代苯基)-10,15,20-三(4-甲基苯基)卟啉，得到的产率可观（83%）。二吡咯烷1与两种适当取代的苯甲醛的混合物反应，能够获得所需的中间取代卟啉，这些产物可以通过闪光色谱法轻松分离。这些卟啉分别带有一个4-乙酰氨基苯基基团2或4-羧甲基苯基基团3，以及三个4-甲基苯基外围功能基团，采用两步一瓶反应法合成，得到的产率显著（15–17%）。对卟啉2和3的碱性水解反应分别生成氨基卟啉4和酸性卟啉5。将卟啉5与醋酸锌反应得到相应的金属复合物Zn-酸性卟啉6。通过酸氯化衍生物（Zn-酸性卟啉6或铁烯乙酸）与氨基卟啉4之间的耦合反应获得二聚体7和8。本策略可以轻松用于制备其他类似的二聚体衍生物。这些化合物在电子材料方面可能具有有趣的应用。对涂有卟啉二聚体7和8的SnO2电极进行的光能转换初步研究显示，二聚体7和8可能适用于太阳能转换设备。
• An Efficient Synthesis of Porphyrins with Different<i>meso</i>Substituents that Avoids Scrambling in Aqueous Media
  作者：Agnieszka Nowak-Król、Rémi Plamont、Gabriel Canard、Judicaelle Andeme Edzang、Daniel T. Gryko、Teodor Silviu Balaban

  DOI：10.1002/chem.201403677

  日期：2015.1.19

  aldehydes: THF/H2O 2:1, [DPM]=13 mM, [aldehyde]=13 mM, [HCl]=150 mM, 3 h) resulted in the formation of porphyrins in yields of 9–38 % without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans‐A2B2‐, A3B‐, and trans‐AB2C‐porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored

  我们已经开发出了新的条件，可以提供区域异构纯的带有芳基和芳基乙炔基取代基的反式A 2 B 2，A 3 B和反式AB 2 C卟啉。卟啉的制备方法是：将二吡咯甲烷与醛进行酸催化缩合，然后用对氯苯醌或2,3-二氯-5,6-二氰基-1,4-苯并醌（DDQ）进行氧化。通过检查各种反应参数（例如溶剂组成，酸浓度和反应时间），可以确定最佳的缩合条件。确定的条件（对于芳族醛：EtOH / H 2 O 4：1，[DPM] = 4 m M，[醛] = 4 mM，[HCl] ＝ 38m M，16小时；m，[m / z] 。对于芳基乙炔醛：THF / H 2 O 2：1，[DPM] = 13 m M，[醛] = 13 m M，[HCl] = 150 m M，3小时）导致卟啉的形成，产率为9 –38％，无可检测的加扰。该合成与各种官能团如酯或腈相容。总共有20个新的trans- A 2 B 2-，A 3 B-和trans-
• Synthesis of galactopyranosyl substituted porphyrins
  作者：Hermann K. Hombrecher、Stefan Ohm、Daniela Koll

  DOI：10.1016/0040-4020(96)00174-3

  日期：1996.4

  The synthesis of several galactopyranosyl substituted porphyrins is described. Starting from porphyrin carboxylic esters (1) di-O-isopropylidene-α-D-galactopyranosyl substituted porphyrins 3a – 3e were synthesised by a transesterification procedure. Treatment of 3a – 3e with TFA/water leads to the formation of galactopyranosyl substituted porphyrins 4a – 4e in excellent yield. Furthermore porphyrin

  描述了几种吡喃半乳糖基取代的卟啉的合成。从卟啉羧酸酯（1）开始，通过酯交换法合成了二-O-异亚丙基-α-D-吡喃半乳糖基取代的卟啉3a-3e。用TFA /水处理3a-3e可以形成产率极高的galactopyranosyl取代的卟啉4a-4e。此外，卟啉3e可以通过二-O-异亚丙基-α-D-吡喃半乳糖基取代的苯甲醛7与吡咯的反应来合成。通过CsF催化6-脱氧-6-溴-二-O-异亚丙基-α-D-吡喃半乳糖6的缩合反应合成醛7 用4-甲酰基苯甲酸。
• An efficient synthesis of tetraaryl porphyrins substituted with ester groups bearing long alkyl chains
  作者：Hermann K. Hombrecher、Stefan Ohm

  DOI：10.1016/s0040-4020(01)86323-7

  日期：1993.3

  The synthesis of tetraaryl porphyrins substituted with long chain ester groups is described. The compounds are conveniently prepared from the methyl ester 1a via a based induced transesterification procedure. The method is also applicable for the synthesis of ester linked diporphyrins.

  描述了被长链酯基取代的四芳基卟啉的合成。该化合物可通过基于基础的酯交换步骤，方便地由甲酯1a制备。该方法也适用于酯连接的双卟啉的合成。