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以焦脱镁叶绿酸-a甲酯为起始原料,选择硝酸铊和空气为氧化剂对其进行氧化,分别在二氢卟吩周环上的3,12和15位上引进了甲酰基和甲酰甲基,与盐酸羟胺肟化后,在N,N-二甲基甲酰胺和三氯三嗪的促进下脱水并顺利地转化为氰基;利用丙二腈与二氢卟吩环上羰基的瑙文格尔反应建立了二氰亚甲基结构,进一步的结构修饰则在色基上完成了多氰基取代.通过叶绿素降解产物周环上的不同位置实施氰基化,合成了一系列未见报道的氰基取代的叶绿素类二氢卟吩衍生物,其化学结构均经UV、IR、~1H NMR及元素分析予以证实;同时也讨论了叶绿素类二氢卟吩氰基化的反应机理,并对部分新化合物的体外光动力活性进行了测试.
Taking pyropheophorbide-a methyl ester as starting material, thallium nitrate and air were chosen as oxidants to oxidize them. The formyl groups were introduced at the 3, 12 and 15 positions of the chlorin cycle respectively Formylmethyl, oxime with hydroxylamine hydrochloride, dehydrated under the promotion of N, N-dimethylformamide and trichlorotriazine and successfully converted to cyano; with the use of malononitrile and the chlorin cycle Noghwenger reaction of carbonyl group has established dicyanomethylene structure, and further structural modification has completed the substitution of polycyano group on the chromophore. Through the cyanation at different positions of the chlorophyll degradation products, a A series of cyano-substituted chlorin-chlorin derivatives have not been reported. Their chemical structures were confirmed by UV, IR, ~ 1H NMR and elemental analysis. Cyano chlorinated chlorin Reaction mechanism, and some of the new compounds in vitro photodynamic activity were tested.