22 Diphyllinの構造と合成
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概要
- 論文の詳細を見る
The structures of diphyllin (4), justicidin A (5) and taiwanin E (6) were found to be incorrect and to have to be revised to structures (1), (2) and (3), respectively, from the chemical and NMR spectral evidences. The benzhydrylsuccinic acid (20) was synthesized and converted, by a 8-step procedure as shown in Chart 1, to the Murakami-diphyllin (9). The selective cyclization of (20) gave cis- and trans-4-(3-bromo-4,5-dimethoxyphenyl)tetralone (28a,b: R=H) as expected, while the cyclization of debromo derivative (19) of (20) gave predominantly a trans-4-(3,4-methylenedioxyphenyl)tetralone (38), which was converted to a 1-hydroxy-2,3-naphthalide (4) by a similar 6-step procedure to (9) as shown in Chart 2. Compound (9) or (4) was found not to be identical with diphyllin. Consideration of the NMR spectra of aromatized 2,3-naphthalide lignans in which the 4-phenyl ring lies perpendicularly to the naphthalene ring and shields the lactone methylene in 1-hydroxy-2,3-naphthalide system (A) afforded an effective method to distinguish between systems (A) and (B) as shown in Table III. The lactone methylene of diphyllin, justicidin A or taiwanin E is obviously not shielded. The syntheses of them were achieved by the procedure shown in Chart 3, and followed by identification with natural samples. All the hitherto known aromatized α-hydroxy-2,3-naphthalide lignans, such as diphyllin, justicidin A, taiwanin E and dehydropodophyllotoxin, are now concluded to have 4-hydroxy-2,3-naphthalide system (B).
- 天然有機化合物討論会の論文
- 1968-09-20
著者
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金 相元
Faculty of Pharmaceutical Sciences, Josai University
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金 相元
Faculty Of Pharmaceutical Sciences Josai University
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堀井 善一
Faculty Of Pharmaceutical Sciences Josai University
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堀井 善一
阪大薬学部
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辻内 源英
Faculty of Pharmaceutical Sciences, Osaka University
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百瀬 雄章
阪大薬学部
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大川 和夫
Faculty Of Pharmaceutical Sciences Osaka University
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大川 和夫
阪大薬学部
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金 相元
阪大薬学部
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辻内 源英
阪大薬学部
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辻内 源英
Faculty Of Pharmaceutical Sciences Osaka University
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百瀬 雄章
Faculty Of Pharmaceutical Sciences Kanazawa University
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