Facile synthesis of 131‐oxo‐porphyrins possessing reactive 3‐vinyl or 3‐formyl group, protochlorophyll‐a/d derivatives by 17,18‐dehydrogenation of chlorins
Facile synthesis of 131‐oxo‐porphyrins possessing reactive 3‐vinyl or 3‐formyl group, protochlorophyll‐a/d derivatives by 17,18‐dehydrogenation of chlorins
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通过二氢卟酚的 17,18-脱氢轻松合成具有活性 3-乙烯基或 3-甲酰基的 131-氧代-卟啉、原叶绿素-a/d 衍生物
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
Tomohiro Miyatake
中科院分区：
文献类型：
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作者：
H. Tamiaki;Takuya Watanabe;Tomohiro Miyatake
通过对易获得的叶绿素-a进行修饰，制备了甲基原卟啉-a/d。关键步骤是131-氧氯氧化生成相应的卟啉，2,3-二氯-5,6-二氰-对苯醌对17,18脱氢有效。氯的氧化电位降低是氧化的必要条件。通过插入锌作为中心金属，还原13-羰基和/或高浓度聚集来实现易氧化。合成的131-氧-卟啉在3位上含有乙烯基和甲酰基。这些基团在分子中非常活跃，并选择性地转化为其他官能团。
Methyl protopyropheophorbides-a/d were prepared by modification of readily available chlorophyll-a. The key step was oxidation of 131-oxo-chlorin to the corresponding porphyrin, and 2,3-dichloro-5,6-dicyano-p-benzoquinone was effective for 17,18-dehydrogenation. A reduction in oxidation potential of the chlorin was necessary for the oxidation. Facile oxidation was achieved by insertion of zinc as the central metal, reduction of the 13-carbonyl group and/or aggregation by high concentration. The synthetic 131-oxo-porphyrins had vinyl and formyl groups at the 3-position. These groups were very reactive in the molecule and selectively converted to other functional groups.