(甲)乙烯基化的叶绿素类二氢卟吩衍生物的合成及其光敏杀菌活性

Synthesis of(Methylenated)vinylated Chlorophyllous Chlorins and Study on Their Photosensitive Bactericidal Activities

以叶绿素-a（b）的最初降解产物脱镁叶绿酸-a（b）甲酯为起始原料,利用其二氢卟吩周环上的活性反应区域,经羟醛缩合、空气氧化和氧化剂氧化等常见的化学反应构建羟甲基或者甲酰基结构,再通过Grignard反应、酸催化脱水和E-环重排反应,在周环的不同位置上引进了具有较高反应活性的甲烯基或者乙烯基,完成了一系列未见报道的多端烯基取代的叶绿素类二氢卟吩衍生物的合成,其化学结构均经UV、IR、^1H NMR及元素分析予以证实;对相应的化学反应提出了可能的反应机理,并对部分新化合物的体外光动力抗菌活性进行了测试.

Pheophorbide-a and b methyl esters, as initial degraded products from chlorophyll-a and b, were used as starting materials, and the hydroxylmethylic or formylic structures were established making use of the active reaction regions on chlorin periphery by some common reactions, such as aldol condensation, allomerization, oxidant oxidation. The methylene or vinyl groups possessing higher reactivity were introduced at different site around chlorin pericycle by Grignard reavtion, acid-catalyzed dehydration and rearrangement reaction in E-ring. A series of unreported chlorophyllous chlorins substituted by multi-terminal alkenyl group were synthesized and their chemical structures were characterized by elemental analysis, UV, IR and ~1H NMR spectra. The in vitro photosensitive bactericidal activities of new chlorins were discussed and the possible mechanisms about corresponding reactions were tentatively proposed.