A strategy for the synthesis of asymmetrically substituted tetraazaanthracene linked bis-porphyrins in which the two porphyrin rings contain differences in their peripheral substituents has been developed. The method is illustrated by the preparation of bis-porphyrins with a single meso-halophenyl and seven meso-3,5-di-tert-butylphenyl substituents. The bis-porphyrins were prepared by condensation of a porphyrin-α-dione with benzene-1,2,4,5-tetraamine to form a porphyrin diaminoquinoxaline intermediate which was subsequently condensed with a second different porphyrin-α-dione. The key issue in the synthesis was the separation of the desired asymmetrically substituted bis-porphyrin from the symmetric bis-porphyrin by-products of similar polarities. Enhanced separation of the bis-porphyrin products was achieved by chelation of a metal into one of the porphyrin rings, the metal being introduced at the porphyrin-α-dione stage. Copper was successfully used when chelated into the less polar porphyrin-α-dione but the use of zinc in the more polar porphyrin-α-dione to enhance bis-porphyrin separation was unsuccessful as the pyridinium hydrochloride produced in the reaction was found to demetallate the porphyrins.
我们开发了一种合成不对称取代的四氮杂
蒽连接双
卟啉的策略,其中两个
卟啉环的外围取代基不同。该方法通过制备具有一个中-卤化苯基和七个中-3,5-二
叔丁基苯基取代基的双
卟啉来说明。双
卟啉的制备方法是将一个
卟啉-α-二酮与
苯-1,2,4,5-四胺缩合,形成一个
卟啉二
氨基
喹喔啉中间体,然后再与第二个不同的
卟啉-α-二酮缩合。合成的关键问题是将所需的不对称取代双
卟啉从极性相似的对称双
卟啉副产物中分离出来。在
卟啉-α-二酮阶段引入
金属,通过在其中一个
卟啉环上螯合
金属来加强双
卟啉产物的分离。在极性较弱的
卟啉-α-二酮中螯合
铜时取得了成功,但在极性较强的
卟啉-α-二酮中螯合
锌以提高双
卟啉的分离效果并不成功,因为在反应中产生的
盐酸吡啶鎓会使
卟啉脱
金属。