叶绿素-α衍生物的芳香性及其Vilsmeier反应

Aromaticity and Vilsmeier reaction of chlorophyll-α deriveatives

以焦脱镁叶绿酸-a甲酯为起始原料,通过3-位乙烯基的四氧化俄氧化和高碘酸钠裂解得到焦脱镁叶绿酸-d甲酯-d,再与戊基溴化镁的格氏反应生成卟吩醇.将其转化为卟吩镍配合物后,与3-N,N-二甲氨基丙稀醛和三氯氧磷进行Vilsmeier反应,得到具有甲酰乙烯基取代的叶绿素衍生物.研讨了焦脱镁叶绿酸-a甲酯的芳香性及其亲电取代反应机理,通过1H NMR、UV-Vis、IR以及元素分析确定了新化合物的化学结构.

Methyl pyropheophorbide-α was used as starting material and was converted into methyl pyro-pheo-phorbide-d oxidation for vinyl group at 3-position by osmium （IV） oxide and sodium perioadant. This chlorin aldehyde was reacted with amyl magnesium bromide to give chlorin alcohol. After generating nickel chlorin, the Vilsmeier reaction with 3-（dimethylamino） acrolein/phosphoryl chloride （3-DMA/POCl3） was carried out to give meso-20-formylvinylchlorin. The relevant reaction mechanisms were tentatively proposed and the structures of new compounds were characterized by elemental analysis, UV, IR and ^1H NMR spectra.