具有叶绿素-a碳架的(细菌)卟吩衍生物的合成及其共轭区域变化对光谱性能的影响  

Synthesis of Bacteriochlorin Derivative with Chlorophyll-a Skeleton and Effect on the Spectra by Change in the Conjugate Region

作　　者：纪建业[1] 王鲁敏[2] 荆济荣[2] 韩光范[3] 王进军[2] 

机构地区：[1]通化师范学院化学系,通化134002 [2]烟台大学应用化学系,烟台264005 [3]江苏科技大学材料科学工程学院,镇江212003

出　　处：《有机化学》2007年第4期494-501,共8页Chinese Journal of Organic Chemistry

基　　金：国家科技部中韩政府间合作研究(2002);山东省技术创新重点(No.200391006008)资助项目.

摘　　要：以脱镁叶绿酸-a甲酯(MP-a)(1)为起始原料,通过四氧化锇和高碘酸钠的氧化给出3-位乙烯基和132-位α-氢的氧化产物2和3,再用四氧化锇继续氧化卟吩醛2则得到细菌卟吩醛4.经脱甲酸甲酯和硝酸铊氧化,MP-a(1)转化为焦脱镁叶绿酸衍生物5,将其进一步用四氧化锇氧化则形成细菌卟吩缩醛6.卟吩醛2在碱性条件下转化为卟吩e6三甲酯7,2与烷基溴化镁的格氏反应给出脱镁叶绿酸醇9,选择高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将3-位羟基氧化成羰基,所生成的卟吩二酮10在酸性条件下脱去甲酸甲酯生成焦脱镁叶绿酸衍生物11,用四氧化锇对7和11实施氧化,则分别转化为细菌卟吩衍生物8和12.同时,讨论了叶绿素衍生物的共轭区域变化对其光谱性能的影响.所合成的新卟吩和细菌卟吩衍生物均经UV,IR,1HNMR及元素分析证明其结构.Methyl pheophorbide-a （MP-a） （1） was used as starting material and was oxidized with osmium（Ⅷ） oxide followed by ethylene glycol cleavage with sodium periodate to give 2 and 3 for oxidizing vinyl group at 3-position and for a-hydrogen at 132-poaition respectively. The chlorin aldehyde 2 was oxidized continually with osmium（Ⅷ） oxide to give bacteriochlorin aldehyde 4. After eliminating for methyl formate and oxidizing with thallium（Ⅲ） nitrate MP-a （1） was converted into pyropheophorbide derivative 5 which was oxidized again with osmium（Ⅷ） oxide to generate becteriochlorin acetal 6. In the basic condition chlorin aldehyde 2 was converted into chlorin e6 derivatives 7. The Grignard reaction of 2 with alkyl magnesium bromide afforded pheophorbide alcohol 9 followed by oxidation with tetrapropylammonium perruthenate （TPAP） and N-methylmorpholine N-oxide to afford chlorin diketoester 10. The conversion of 10 from pheophorbide to pyropheophorbide was completed in acid condition by refluxing to form methyl 3-alkylcarbonyl-3-devinylpyropheophorbide-a 11. The chlorin e6 7 and chlorin 11 were oxidized further with osmium（VIII） oxide in the same oxidization condition to yield bateriochlorin 8 and 12, respectively. The ef- fect on the spectra by change in the conjugate region was discussed. The structures of the compounds were characterized by elemental analysis, UV, IR and ^1H NMR spectra.

关 键 词：叶绿素-A 衍生物 卟吩 细菌卟吩 氧化反应 光动力疗法(PDT) 

分 类 号：O626[理学—有机化学]