A simple method for efficient synthesis of tetrapyridyl-porphyrin using Adler method in acidic ionic liquids
A simple method for efficient synthesis of tetrapyridyl-porphyrin using Adler method in acidic ionic liquids
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DOI：
10.1039/c4ra02522a
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发表时间：
2014-01-01
期刊：
影响因子：
3.9
通讯作者：
Ishikawa, Yuichi
中科院分区：
文献类型：
--
作者：
Kitaoka, Satoshi;Nobuoka, Kaoru;Ishikawa, Yuichi
本文研究了几种酸性离子液体[HC（4）im] [X]（X- = CF_3SO_3 ~-、Cl_4 ~-、Cl ~-、CF_3CO_2 ~-和BF_4 ~-）作为酸性催化介质合成四苯基卟啉（TPP）。对于这样的离子液体，[HC（4）im][X]的阴离子（X-）与离子液体的酸性有关，并且影响卟啉的形成。这种酸性离子液体的合成方法也适用于其他meso取代苯基卟啉和5，10，15，20-四（4-吡啶基）-21 H，23 H-卟啉（TPyP），它在4个meso位置上具有4-吡啶基结构。在[HC（4）im][CF_3CO_2]中，TPyP的产率为11%，且[HC（4）im][CF_3CO_2]可重复使用3次以上而不损失催化活性。与传统的桤木方法相比，使用酸性离子液体的TPyP合成方法可以通过简单的过滤从TPyP中除去离子液体，传统的Alder方法需要真空蒸馏或液-液萃取来除去丙酸。我们提出的使用酸性离子液体制备卟啉的方法具有广泛的应用前景。
We investigated the preparation of tetraphenylporphyrin (TPP) using the several acidic ionic liquids, [HC(4)im] [X] (X- = CF3SO3-, ClO4-, Cl-, CF3CO2-, and BF4-), as acid catalytic media. For such ionic liquids, the anion (X-) of [HC(4)im][X] is related to the acidity of the ionic liquid, and affects porphyrin formation. This synthetic method using acidic ionic liquids can also be applied to other meso-substituted phenyl porphyrins and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP), which has 4-pyridyl moieties at four meso positions. In [HC(4)im][CF3CO2], TPyP could be obtained in 11% yield, and the [HC(4)im][CF3CO2] could be reused at least 3 times without any loss of its catalytic activity. The TPyP synthesis methodology using acidic ionic liquids can remove the ionic liquids from TPyP by easy filtration in contrast to the traditional Alder method, which needs vacuum distillation or liquid-liquid extraction for removing propionic acid. Our proposed porphyrin preparation method using the acidic ionic liquids potentially have wide applications to various useful porphyrin analogues.