Molecular design and synthesis of coumarin by indexing

香豆素的分子设计与索引合成

• 批准号: 01571141
• 负责人: HARAYAMA Takashi
• 金额: $ 1.41万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01571141/
• 关键词: Salicylaldehyde; Wittig reagent; Coumarin synthesis; Substituent effect; Reisch's coumarin; 5, 8-Dimethoxycoumarin; 7, 8-Dimethoxycoumarin; Structure revision; 7.8ージメトキシクマリン; 構造訂正; クマリン生成; ライシュクマリン; トダレノン; 5ーメトキシシュベレノン; ウイッテイッヒ反応; 反応温度; ケイ

1)Development of a novel synthetic method of salicylaldehyde(1)Claisen rearrangement of aryl propargyl ether in the presence of CsF afforded exclusively an arylfuran, which was converted to salicylaldehyde(1)by successive treatment with OsO_4 NaIO_4 and aq. NaHCO_3 in good yield. oxidation oy the furan ring with ozone was more convenient and effective.2)Convenient synthesis of coumarin(2)by reaction of with wittig reagent Reaction of 1 with Ph_3 P=CHCOOEt in diethylaniline under reflux gave coumarin(2)in a high yield. Tae methoxy substituent at C_4 on 1 facilitated the formation of coumarin ring in comparison with the methoxy group at other positions.3)Structural elucidation of naturally occurring coumarins by syntheses In connection with synthetic studies on Reisch's coumarin, coumarins(3 and 4)were synthesized by utilizing novel methods mentioned above. Moreover, the coumarin isolated from a Compositae plant by Dopke was synthetically proven to be 7, 8-dimethoxycoumarin, not 5, 8-dimethoxycoumarin.

1)开发一种新的水杨醛合成方法(1)在CsF存在下芳基炔丙醚发生克莱森重排仅得到芳基呋喃,通过OsO_4 NaIO_4和水溶液连续处理将其转化为水杨醛(1)。 NaHCO_3收率良好。 2)与维蒂希试剂反应方便合成香豆素(2) 1与Ph_3 P=CHCOOEt在二乙基苯胺中回流反应得到香豆素(2),收率较高。与其他位置的甲氧基相比，1位C_4上的Tae甲氧基取代基更容易形成香豆素环。3）通过合成阐明天然香豆素的结构结合Reisch香豆素的合成研究，利用上述新方法合成了香豆素（3和4）。此外，Dopke从菊科植物中分离出来的香豆素经合成证明是7, 8-二甲氧基香豆素，而不是5, 8-二甲氧基香豆素。

项目成果

Hisashi ISHII: "Synthetic Studies on Naturally Occurring Coumarins(I) A Convenient Synthesis of 5,8ーdimethoxyー and 7,8ーDimethoxydoumarins" Chemical and Pharmaceutical Bulletin.

Hisashi ISHII：“天然香豆素的合成研究 (I) 5,8-二甲氧基-和 7,8-二甲氧基香豆素的便捷合成”化学和制药通报。

H. Ishii: "A Convenient Synthesis of a Simple Coumarin" Chem. Pharm. Bull.31. 3100 (1991)

H. Ishii：“简单香豆素的便捷合成”化学。

Hisashi ISHII: "A Convenient Synthesis of a Simple Coumarin" Chemical and Pharmaceutical Bulletin. 31. 3100-3102 (1991)

Hisashi ISHII：“简单香豆素的便捷合成”化学和药物通报。

H. Ishii: "Synthetic Studies on Naturally Occurring Coumarins (1) A Convenient Synthesis of 5, 8-Dimethoxy- and 7, 8-Diemthoxycoumarins" Chem. Pharm. Bull.

H. Ishii：“天然存在的香豆素的合成研究 (1) 5, 8-二甲氧基-和 7, 8-二甲氧基香豆素的便捷合成” Chem。

Hisashi ISHII: "Synthetic Studies on Naturally Occurring Coumarins (1) A Convenient Synthesis of 5,8-dimethoxy- and 7,8-Dimethoxydoumarins" Chemical and Pharmaceutical Bulletin.

Hisashi ISHII：“天然香豆素的合成研究 (1) 5,8-二甲氧基-和 7,8-二甲氧基香豆素的便捷合成”化学和制药通报。