δ-(甲酰乙烯基)二氢卟吩衍生物的合成

Synthesis of Derivatives of δ-(2-Formylvinyl)-chlorins

以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)δ-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742nm.同时保留了对δ-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.

Starting from methyl pheophorbide-a, the derivatives of δ-（2-formylvinyl）-chlorins were synthesized by Vilsmeier reaction. The nickel（Ⅱ） methyl pheophorbide-a or nickel（Ⅱ） methyl purpurin-18 reacted with 3-（dimethylamino）-acrolein/phosphoryl chloride to give nickel（Ⅱ） δ-（2-formylvinyl）-purpurin-7-trimethyl ester or nickel（Ⅱ） 3-（2-formylvinyl）-chlorin P6 trimethyl ester. When nickel（Ⅱ） purpurin-18 imide reacted with Vilsmeier agent, the derivatives of nickel（Ⅱ） δ-（2-formylvinyl）-purpurin-18 imide were obtained. By treatment of the derivatives of nickel（H） δ-（2-formylvinyl）-chlorin with trifluoroacetic acid, the removal of central nickel（Ⅱ） ion was accomplished. The derivatives of δ-（2-formylvinyl）-chlorin demonstrated a considerable bathochromic shift of the major absorption band in the red region of the optical spectrum. The maximal UV/vis absorption of δ-（2-formylvinyl）-purpurin-18 imide was 742 nm. The structures of all new compounds were characterized by elemental analysis, UV, IR, MS and ^1H NMR spectra.