2-氢醌卟啉合成中的结构效应

Structural effect in synthesis of 2-hydroquinoneporphyrin

在2-硝基四取代基苯基卟啉及其金属配合物(简称2-NO2,MTRPP)与对苯二酚直接合成2-(2,5-二羟基苯基)MTRPP(简称2-氢醌卟啉)的反应中,原料锌卟啉配合物的产率明显低于其它金属配合物;当四个中位苯环的对位存在羟基时,产率大幅提高;当四个中位苯环的对位存在甲氧基时,产率下降.中心离子的配位键、中位苯环取代基的结构特点通过电子效应、空间效应及至反应机理等途径对相关反应产生重大影响.

A series of 2-hydroquinoneporphyrins and their metal complexes were synthesised by direct reactions of 2-nitro-5,10,15,20-tetraphenylporphyrins and their metal complexes（2-NO2MTPP） to hydroquinone. The results show that the yields of their corresponding Zn （ Ⅱ ） complexes are markedly on the low side,and the yields of their corresponding tetra（4-hydroxypheny1）porphyrin are markedly on the increase, and the yields of their corresponding tetra （4-methoxypheny1）porphyrin are markedly on the decrease. The coordinate bond of metallic ions in 2-NO2MTPP and structural feature of substituents on meso-pheny1 ring of 2 - NO2MTPP have marked influence on their relevant reactions for the electronic effect,steric strain and reaction mechanism.