红紫素-18二酰亚胺的羟(酰)基化及其叶绿素类二氢卟吩衍生物的合成
收稿日期: 2014-05-06
修回日期: 2014-06-13
网络出版日期: 2014-09-12
基金资助
国家自然科学基金(No.21272048)和山东省黄金工程技术研究中心(2011年度)资助项目.
Hydroxyla(acyla)tion of Purpurin-18 Imide and Synthesis of Chlorophyllous Chlorin Derivatives
Received date: 2014-05-06
Revised date: 2014-06-13
Online published: 2014-09-12
Supported by
Project supported by the National Natural Science Foundations of China (No.21272048) and the Project of Shandong Applied Reaearch Centre of Gold Nanotechnology (2011).
以红紫素-18甲酯为起始原料, 通过外接环的胺解反应转化成氮上连有含羟基或者酰基取代结构的红紫素-18二酰亚胺, 利用其周环上的活性反应区域, 通过氧化、空气氧化、游离基取代和亲核取代反应, 在3-, 12-和20-meso-位上分别引进了羟基、酰基或者带有相应官能结构的取代基团, 完成了12个未见报道的具有红紫素-18二酰亚胺的叶绿素类二氢卟吩衍生物的合成, 其化学结构均经UV, IR, 1H NMR及元素分析予以证实; 同时也讨论了不同位置的羟基化和酰基化对四吡咯大环所形成的不同影响.
关键词： 叶绿素-a; 二氢卟吩; 红紫素-18二酰亚胺,化学修饰; 合成
纪建业 , 殷军港 , 赵丽丽 , 姚楠楠 , 祁彩霞 , 王进军 . 红紫素-18二酰亚胺的羟(酰)基化及其叶绿素类二氢卟吩衍生物的合成[J]. 有机化学, 2014 , 34(11) : 2262 -2271 . DOI: 10.6023/cjoc201405009
Purpurin-18 methyl ester, as a starting material, was converted into purpurin-18 imide linked substituted structures bearing hydroxyl or acyl group at nitrogen atom in the imide by aminolysis for exocyclic ring. The hydroxyl, acyl or substituted groups with relevant functional structures were introduced by oxidation, allomerization, radical substitution and nucleophilic substitution reaction making use of active reactive regions on the periphery. The syntheses of 12 unreported chlorophyllous chlorins with carbon skeleton of purpurin-18 imide were accomplished and their chemical structures were characterized by UV, IR, 1H NMR and elemental analysis. The different effects on the tetrapyrrol macrocycle by hydroxylation and acylation are discussed.
Key words： chlorophyll-a; chlorin; purpurin-18 imide; chemical modification; synthesis
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