Synthesis of asymmetricallymeso-substituted porphyrins bearing amino groups as potential cationic photodynamic agents

化学 卟啉 苯甲醛 阳离子聚合 三氟乙酸 产量(工程) 药物化学 三氟甲基 二氯甲烷 吡咯 催化作用 缩合反应 有机化学 溶剂 材料科学 冶金 烷基
作者
Daniel A. Caminos,Edgardo N. Durantini
出处
期刊:Journal of Porphyrins and Phthalocyanines [World Scientific]
卷期号:09 (05): 334-342 被引量:23
标识
DOI:10.1142/s1088424605000423
摘要

Novel asymmetrically meso-substituted porphyrins bearing amino groups have been synthesized as precursors of cationic photodynamic agents. The amphiphilic character of these porphyrins was increased by the presence of a high lipophilic trifluoromethyl group. Different patterns of porphyrin structures were obtained from meso-4-[(3- N , N -dimethylaminopropoxy)phenyl] dipyrromethane 1, which was formed by the condensation of 4-(3- N , N -dimethylaminopropoxy) benzaldehyde with a large excess of pyrrole. This reaction takes place at high temperature with a yield of 59%. This reaction was also attempted under acid-catalyzed condensation at room temperature. However, under these conditions, the amino group reduces the catalyst and the reaction does not take place. To obtain porphyrins, dipyrromethane 1 was condensed with aldehydes in the presence of trifluoroacetic acid ( TFA ) under different conditions. First, 1 reacted with 4-(3- N , N -dimethylaminopropoxy)benzaldehyde in dichloromethane catalyzed by TFA (∼4 times TFA /1 molar ratio) to obtain 6.2% of 5,10,15,20-tetrakis(4-[3- N , N -dimethylaminopropoxy]phenyl)porphyrin ( A 4 -porphyrin). Under similar conditions, reaction of 1 with 4-(trifluoromethyl)benzaldehyde produces 5,15-di(4-[3- N , N -dimethylaminopropoxy]phenyl)-10,20-di(4-trifluoromethylphenyl)porphyrin ( A 2 B 2 - porphyrin ) with a 4.8% yield. This procedure also yields a mixture of porphyrins, which were formed due to acidolysis of 1. When a minor amount of TFA was used in acetonitrile, the yield of A 2 B 2 -porphyrin was very poor (∼0.4%). On the other hand, condensation of 1 with 4-trifluoromethylbenzaldehyde and 4-(3- N , N -dimethylaminopropoxy)benzaldehyde catalyzed by TFA (∼2 times TFA /1 molar ratio) in acetonitrile yields 9.3% of 5-(4-trifluoromethylphenyl)-10,15,20-tris(4-[3- N , N -dimethylaminopropoxy]phenyl)porphyrin ( A 3 B-porphyrin ). A 2 B 2 and A 4 porphyrins were also isolated with 6.0 and 2.0%, respectively. Finally, exhaustive methylation of amino porphyrins produces cationic sensitizers (>94% yield). Absorption and fluorescence spectroscopic studies of these sensitizers were compared in N , N -dimethylformamide. In these porphyrins, the cationic centers are isolated from the porphyrin ring by a propoxy bridge. Thus, the cationic charges have minimal influence on the photophysical properties of the sensitizers. In addition, this chain provides a higher mobility of the charge, which could facilitate interaction with the outer membrane of the Gram-negative bacteria. These amphiphilic cationic porphyrins are promising photosensitizers with potential applications in bacterial inactivation by photodynamic therapy.
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