二氢卟吩醛的格氏反应及其3-位苯基取代叶绿素衍生物的合成  

Grignard Reaction of Aldehyde Chlorin and Synthesis of Chlorophyll Derivatives Substituted with Phenyl Group at 3-Position

作　　者：赵丽丽[1] 王朋[2] 刘超[2] 张朋[2] 王进军[1] 

机构地区：[1]烟台大学化学生物理工学院,山东烟台264005 [2]烟台大学药学院,山东烟台264005

出　　处：《烟台大学学报（自然科学与工程版）》2010年第3期176-182,共7页Journal of Yantai University(Natural Science and Engineering Edition)

基　　金：山东省自然科学基金资助项目(Y2008B49)

摘　　要：以焦脱镁叶绿酸-a甲酯为起始原料得到3-甲酰基焦脱镁叶绿酸-a甲酯(4),与苄基溴化镁进行Grignard反应将其3-位甲酰基转化为1-羟苄基.选用高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物混合氧化剂实施氧化而生成3-位苯乙酰基焦脱镁叶绿酸衍生物(6).再与苄基溴化镁进行Grignard反应,分别得到二氢卟吩叔醇(7)和二氢卟吩仲醇(5);在干燥苯中酸催化对化合物7实施脱水,给出cis-结构的3-位双苯基取代的焦脱镁叶绿酸-a甲酯衍生物(8),采用相同的格氏和脱保护反应,分离出二苯基取代二氢卟吩酮醇(9).所合成的3-位苯基取代的新叶绿素类二氢卟吩衍生物的化学结构均经UV,1H NMR及元素分析予以证明.The 3-vinyl-methyl pyropheophorbide-a（4） derivative is synthesized from methyl pyropheophorbide as starting material.The formyl group is converted into 1-hudroxyalkyl group by Grignard reaction with benzyl magnesium bromide.The hydroxyl group of sec-alcohol chlorin is oxidized by mixed oxidizing agent of tetrapropylammonium perruthenate（TPAP） and N-methylmorpholine N-oxide to give 3-phenylacetyl pyropheo-phorbide-a derivative（6）.The second Grignard reaction of this keto chlorin with benzyl magnesium bromide is carried out to yield the tert-alcohol chlorin（7） and the sec-alcohol chlorin（5）.The following dehydration of alcohol chlorins are performed for compound 7 in dry benzene by refluxing to form cis-form methyl pyropheophorbide-a derivatives（8）.Diphenyl substituted chlorin ketol（9） is separated in the same Grignard reaction and dehydration reaction.The structures of the new compounds are characterized by elemental analysis,UV,and 1H NMR spectra.

关 键 词：叶绿素-a衍生物 苯基取代焦脱镁叶绿酸-a甲酯 Grignard反应 光动力疗法(PDT) 

分 类 号：O62[理学—有机化学]