Synthesis of two aromatic methylenedioxy-substituted colchicine congeners: elucidation of the structure of cornigerine as 2,3-(methylenedioxy)-2,3-didemethoxycolchicine
Synthesis of two aromatic methylenedioxy-substituted colchicine congeners: elucidation of the structure of cornigerine as 2,3-(methylenedioxy)-2,3-didemethoxycolchicine
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两种芳香族亚甲二氧基取代的秋水仙碱同系物的合成：阐明秋水仙碱为 2,3-(亚甲二氧基)-2,3-二脱甲氧基秋水仙碱的结构
DOI：
10.1021/jo00331a021
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发表时间：
1981
影响因子：
3.6
通讯作者：
A. Brossi
中科院分区：
文献类型：
--
作者：
M. Roesner;F. Hsu;A. Brossi
在80-90 ℃下用浓硫酸处理秋水仙碱，除2-去甲基秋水仙碱外，还得到可分离和鉴定的儿茶酚-秋水仙碱混合物。类似的处理1-去甲基和3-去甲基秋水仙碱主要产生1，2-邻苯二酚或其2，3异构体。这些儿茶酚的亚甲基化得到秋水仙碱同系物1和10。与天然的Cornigerine比较表明，该生物碱与2，3-亚甲二氧基化合物10相同，而与以前提出的化合物1不同。Cornigerine是Santavy等于1961年从秋水仙属（Colchium cornigerum）中分离得到的生物碱，具有与秋水仙碱相似的生物活性。3山茱萸碱的结构1，在NMR分析和化学降解的基础上提出，用1，2-亚甲二氧基环与秋水仙碱的芳环A成环，取代了两个原始的甲氧基4（见结构1和10）。值得注意的是，
Treatment of colchicine with concentrated sulfuric acid at 80-90 C afforded besides 2-demethylcolchicine a mixture of catecholiccolchicines which could be separated and identified. Similar treatmentof 1-demethyland 3-demethylcolchicine gave predominantly the 1, 2-catechol or its 2, 3 isomer. Methylenation of these catechols afforded the colchicine congeners 1 and 10. A comparison with natural cornigerine revealed that the alkaloid was identical with the 2, 3-methylenedioxy compound 10 and notwith 1, as formerly proposed.Cornigerine, an alkaloid from Colchium cornigerum species, was isolated by Santavy et al. in 19612 and reported to exhibit similar biological activities as colchicine. 3 Structure 1 for cornigerine, with a 1, 2-methylenedioxy ring annulated to the aromatic ring A of colchicine replacing the two original methoxy groups, was proposed on the basis of a NMR analysis and by chemical degradation4 (see structures 1 and 10). It is interesting to note that the