焦脱镁叶绿酸的炔化反应及其叶绿素类二氢卟吩的合成
收稿日期: 2012-05-02
修回日期: 2012-05-29
网络出版日期: 2012-06-05
基金资助
国家自然科学基金(No. 20972036 )和山东省自然科学基金(No. Y2008B49)资助项目.
Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives
Received date: 2012-05-02
Revised date: 2012-05-29
Online published: 2012-06-05
Supported by
Project supported by the National Natural Science Foundations of China (No. 20972036) and the Natural Science Foundation of Shandong Province of China (No. Y2008B49).
以焦脱镁叶绿酸-a甲酯为起始原料, 利用加成和氧化反应将其转化成3-甲酰基或者3-乙酰基取代和E-环保护的反应前体, 通过Grignard反应在3-位上引进炔基并构建了叔醇或者仲醇结构, 再经脱水和氧化反应生成端位烯炔和炔酮取代的二氢卟吩衍生物. 3-甲酰基焦脱镁叶绿酸-a甲酯与癸基溴化镁的Grignard反应、E-保护和C(3)-羟基的氧化反应得到C(3)-长链烷酰基取代的焦脱镁叶绿酸-a甲酯, 再经酸催化脱水则得到含有链间烯炔结构的二氢卟吩. 首次报道的叶绿素类二氢卟吩衍生物均经UV, IR, 1H NMR及元素分析确定其化学结构, 对相应的化学反应也提出了可能的反应机理.
殷军港 , 王振 , 杨泽 , 金英学 , 王进军 . 焦脱镁叶绿酸的炔化反应及其叶绿素类二氢卟吩的合成[J]. 有机化学, 2012 , 32(10) : 1936 -1943 . DOI: 10.6023/cjoc201205002
Methyl pyropheophorbide-a was used as starting material and converted into 3-formyl or 3-acetyl substituted and E-ring protected reactive precursors. The Grignard reactions of these carbonyl groups introduced alkynyl groups at 3-position to build the tert-alcohol or sec-alcohol structures. Further dehydrations and oxidations produced terminal eneyne and ketyne substituted chlorins, respectively. The pyropheophorbide-a with long chain alkyl group at 3-position was obtained by Grignard reaction with decyl magnesium bromide, protection for E-ring and oxidation of C(3)-hydroxyl group from 3-formylpyropheo- phorbide-a, converted into chlorin containing eneyne moiety in chain by acid-catalyzed dehydration. The structures of all new chlorin derivatives were characterized by elemental analysis, UV, IR and 1H NMR spectra. The possible mechanisms about corresponding reactions were tentatively proposed.
Key words： chlorophyll-a; pyropheophorbide; chlorin; alkynylation; chemical modification
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